TW201510283A - Etching agent, etching method and etching agent formulation - Google Patents
Etching agent, etching method and etching agent formulation Download PDFInfo
- Publication number
- TW201510283A TW201510283A TW103123110A TW103123110A TW201510283A TW 201510283 A TW201510283 A TW 201510283A TW 103123110 A TW103123110 A TW 103123110A TW 103123110 A TW103123110 A TW 103123110A TW 201510283 A TW201510283 A TW 201510283A
- Authority
- TW
- Taiwan
- Prior art keywords
- etchant
- titanium
- hydrogen peroxide
- metal
- copper
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 120
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title abstract description 14
- 238000009472 formulation Methods 0.000 title abstract 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 316
- 229910052751 metal Inorganic materials 0.000 claims abstract description 196
- 239000002184 metal Substances 0.000 claims abstract description 196
- 239000010936 titanium Substances 0.000 claims abstract description 164
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 105
- 239000004065 semiconductor Substances 0.000 claims abstract description 67
- 239000000758 substrate Substances 0.000 claims abstract description 62
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002738 chelating agent Substances 0.000 claims abstract description 55
- 239000007864 aqueous solution Substances 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 36
- 150000007524 organic acids Chemical class 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 31
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims description 151
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 142
- 229910052802 copper Inorganic materials 0.000 claims description 142
- -1 methylene phosphonic acid Chemical compound 0.000 claims description 81
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 63
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 46
- 238000002360 preparation method Methods 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical group O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 5
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- FVHAWXWFPBPFOS-UHFFFAOYSA-N 1,2-dimethyl-3-nitrobenzene Chemical group CC1=CC=CC([N+]([O-])=O)=C1C FVHAWXWFPBPFOS-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 46
- 239000003795 chemical substances by application Substances 0.000 abstract description 32
- 229910045601 alloy Inorganic materials 0.000 abstract description 22
- 239000000956 alloy Substances 0.000 abstract description 22
- 239000010953 base metal Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 47
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 29
- 239000005751 Copper oxide Substances 0.000 description 29
- 229910000431 copper oxide Inorganic materials 0.000 description 29
- 238000004458 analytical method Methods 0.000 description 24
- 235000012431 wafers Nutrition 0.000 description 24
- 229910021642 ultra pure water Inorganic materials 0.000 description 23
- 239000012498 ultrapure water Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- 238000002474 experimental method Methods 0.000 description 17
- 125000000217 alkyl group Chemical group 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 238000004090 dissolution Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 159000000000 sodium salts Chemical class 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000010931 gold Substances 0.000 description 9
- 239000003002 pH adjusting agent Substances 0.000 description 9
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 150000005215 alkyl ethers Chemical class 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 230000002411 adverse Effects 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 239000003945 anionic surfactant Substances 0.000 description 6
- 229960003237 betaine Drugs 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010828 elution Methods 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000012286 potassium permanganate Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
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- 239000010937 tungsten Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
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- 239000012153 distilled water Substances 0.000 description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 3
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
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- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 3
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- 239000004593 Epoxy Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910005540 GaP Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- 230000005764 inhibitory process Effects 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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- 239000011572 manganese Substances 0.000 description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 230000001590 oxidative effect Effects 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 2
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
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- HMNDRWDQGZZYIC-UHFFFAOYSA-N [2-(phosphonomethylamino)ethylamino]methylphosphonic acid Chemical compound OP(O)(=O)CNCCNCP(O)(O)=O HMNDRWDQGZZYIC-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005600 alkyl phosphonate group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- HPDFFVBPXCTEDN-UHFFFAOYSA-N copper manganese Chemical compound [Mn].[Cu] HPDFFVBPXCTEDN-UHFFFAOYSA-N 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- NJGVXNDHVPXKBQ-UHFFFAOYSA-N diazanium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [NH4+].[NH4+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC NJGVXNDHVPXKBQ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- KGOGNDXXUVELIQ-UHFFFAOYSA-N dioctadecylazanium;chloride Chemical compound Cl.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC KGOGNDXXUVELIQ-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- OZYJVQJGKRFVHQ-UHFFFAOYSA-L dipotassium trioxidophosphanium Chemical compound [K+].[K+].[O-]P([O-])=O OZYJVQJGKRFVHQ-UHFFFAOYSA-L 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- BIXHRBFZLLFBFL-UHFFFAOYSA-N germanium nitride Chemical compound N#[Ge]N([Ge]#N)[Ge]#N BIXHRBFZLLFBFL-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- RNYJXPUAFDFIQJ-UHFFFAOYSA-N hydron;octadecan-1-amine;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[NH3+] RNYJXPUAFDFIQJ-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- HIQXJRBKNONWAH-UHFFFAOYSA-N methylidenephosphane Chemical compound P=C HIQXJRBKNONWAH-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- ZRBSSYMJCKNFFZ-UHFFFAOYSA-N octadecylhydrazine Chemical compound CCCCCCCCCCCCCCCCCCNN ZRBSSYMJCKNFFZ-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 1
- 229940116985 potassium lauryl sulfate Drugs 0.000 description 1
- HSJXWMZKBLUOLQ-UHFFFAOYSA-M potassium;2-dodecylbenzenesulfonate Chemical compound [K+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HSJXWMZKBLUOLQ-UHFFFAOYSA-M 0.000 description 1
- LTEGPHVAWSIRGZ-UHFFFAOYSA-M potassium;4-octoxy-4-oxo-3-sulfobutanoate Chemical compound [K+].CCCCCCCCOC(=O)C(S(O)(=O)=O)CC([O-])=O LTEGPHVAWSIRGZ-UHFFFAOYSA-M 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
Description
本發明係關於具有鈦(以下有簡稱為Ti的情況)系金屬的半導體基板之鈦系金屬的加工，更詳而言之，係關於例如具有金屬鈦、鈦-鎢(以下有簡稱為TiW的情況)合金等鈦系金屬以及在該鈦系金屬的上部之金屬銅或銅合金之半導體基板上的鈦系金屬用蝕刻劑及蝕刻方法等。 The present invention relates to the processing of a titanium-based metal having a semiconductor substrate of titanium (hereinafter abbreviated as Ti), and more specifically, for example, has titanium metal, titanium-tungsten (hereinafter referred to as TiW for short). In the case, a titanium-based metal such as an alloy, an etchant for a titanium-based metal on a semiconductor substrate of a metal copper or a copper alloy on the upper portion of the titanium-based metal, an etching method, and the like.
以矽半導體為代表之半導體元件，正因應高性能化、小型化等市場需求，而持續朝細微化、高積體化進展。伴隨細微化、高積體化，作為形成細微配線圖形的金屬，主要係使用配線電阻少的銅。作為對如此的銅配線之阻隔層，已知有含金屬鈦之金屬層(金屬膜)、含金屬鎢之金屬層(金屬膜)、該等金屬的合金層(合金膜)。 The semiconductor components represented by the semiconductors are progressing toward miniaturization and high integration in response to market demands such as high performance and miniaturization. With the miniaturization and high integration, it is mainly used as a metal for forming a fine wiring pattern, which uses copper having a small wiring resistance. As a barrier layer for such a copper wiring, a metal layer (metal film) containing metal titanium, a metal layer (metal film) containing metal tungsten, and an alloy layer (alloy film) of these metals are known.
金屬配線的形成製程，需蝕刻構成如此的阻隔層之金屬，以往作為用以蝕刻該等金屬的蝕刻液，係例如使用氟酸與過氧化氫的混合液、磷酸與過氧化氫的混合液等酸性的蝕刻液等。 In the forming process of the metal wiring, it is necessary to etch the metal constituting the barrier layer. Conventionally, as an etching liquid for etching the metal, for example, a mixed solution of hydrofluoric acid and hydrogen peroxide, a mixed solution of phosphoric acid and hydrogen peroxide, or the like is used. Acidic etching solution, etc.
然而，就過氧化氫而言，例如銅、銀、金等 金屬會促進過氧化氫的分解，因此已知包含過氧化氫的蝕刻液係有溶液壽命短、需適當地控制蝕刻液中過氧化氫的濃度等問題點。 However, in the case of hydrogen peroxide, such as copper, silver, gold, etc. Since the metal promotes the decomposition of hydrogen peroxide, it is known that the etching liquid containing hydrogen peroxide has a problem that the solution has a short life and it is necessary to appropriately control the concentration of hydrogen peroxide in the etching liquid.
而且，包含過氧化氫的蝕刻液，除過氧化氫分解的問題點外，已知還有會氧化銅配線的表面、腐蝕銅配線等金屬配線等的問題點。 Further, in addition to the problem of decomposition of hydrogen peroxide, the etching liquid containing hydrogen peroxide is known to have problems such as a surface of a copper oxide wiring and a metal wiring such as a copper wiring.
作為著眼於此種問題點的蝕刻液或蝕刻劑，以往已知例如：一種包含特定量的過氧化氫與特定量的磷酸鹽的蝕刻TiW用蝕刻液(例如專利文獻1等)；一種包含含有過氧化氫與螫合劑的溶液的半導體基板上之Ti系膜用蝕刻劑(例如專利文獻2等)；一種包含特定量的過氧化氫與特定量的膦酸系化合物的表面處理劑(例如專利文獻3等)；一種蝕刻鎢及/或鈦-鎢合金用之蝕刻液，其係在配線或具有電極用的良好導電性的金屬之存在下至少含有過氧化氫水及鹼性成分，pH為7以下(例如專利文獻4等)；一種蝕刻劑，其係pH為3.0以上7.0以下的酸性的水溶液，含有過氧化氫、鹼金屬離子及防鏽劑(例如專利文獻5等)；一種蝕刻劑，其係pH超過7.0但為8.0以下之鹼性水溶液之含有以過氧化氫及苛性鹼為供應源之鹼金屬離子(例如專利文獻5等)；一種鈦或鈦合金皮膜的蝕刻液，其係在不會被蝕刻的金屬的存在下用以蝕刻鈦或鈦合金之蝕刻液，係包含特定量的過氧化氫、特定量的磷酸、特定量的膦酸系化合物及氨的水溶液(例如專利文獻6等)；一種半導體基板用蝕刻劑，其係包含至少含有過氧化氫、具有羥基的 膦酸系螫合劑及鹼性化合物、以及銅抗蝕劑或/及特定量的具有羥基的膦酸系螫合劑以外的不具有氧化力的2種以上的陰離子物種之溶液(例如專利文獻7等)等。 As an etching liquid or an etchant that focuses on such a problem, for example, an etching liquid for etching TiW containing a specific amount of hydrogen peroxide and a specific amount of phosphate (for example, Patent Document 1) is known. An etchant for a Ti-based film on a semiconductor substrate of a solution of hydrogen peroxide and a chelating agent (for example, Patent Document 2); a surface treating agent (for example, a patent containing a specific amount of hydrogen peroxide and a specific amount of a phosphonic acid-based compound) Document 3, etc.; an etching solution for etching tungsten and/or a titanium-tungsten alloy, which contains at least hydrogen peroxide water and an alkaline component in the presence of a wiring or a metal having good conductivity for an electrode, and has a pH of 7 or less (for example, Patent Document 4); an etchant which is an acidic aqueous solution having a pH of 3.0 or more and 7.0 or less, and contains hydrogen peroxide, an alkali metal ion, and a rust preventive agent (for example, Patent Document 5); An alkaline aqueous solution containing hydrogen peroxide and caustic as a supply source of an alkaline aqueous solution having a pH of more than 7.0 but not more than 8.0 (for example, Patent Document 5); an etching solution for a titanium or titanium alloy film, Not in An etching solution for etching titanium or a titanium alloy in the presence of an etched metal, comprising a specific amount of hydrogen peroxide, a specific amount of phosphoric acid, a specific amount of a phosphonic acid compound, and an aqueous solution of ammonia (for example, Patent Document 6, etc.); An etchant for a semiconductor substrate, comprising at least hydrogen peroxide and having a hydroxyl group a solution of two or more anionic species having no oxidizing power other than a phosphonic acid chelating agent and a basic compound, and a copper resist or/and a specific amount of a phosphonic acid chelating agent having a hydroxyl group (for example, Patent Document 7, etc.) )Wait.
[專利文獻1]：日本特開2000-311891號公報 [Patent Document 1]: JP-A-2000-311891
[專利文獻2]：日本特開2002-155382號公報 [Patent Document 2]: JP-A-2002-155382
[專利文獻3]：日本特開2003-328159號公報 [Patent Document 3]: JP-A-2003-328159
[專利文獻4]：日本特開2004-31791號公報 [Patent Document 4]: JP-A-2004-31791
[專利文獻5]：日本特開2005-163108號公報 [Patent Document 5]: JP-A-2005-163108
[專利文獻6]：日本特開2005-320608號公報 [Patent Document 6]: JP-A-2005-320608
[專利文獻7]：WO2009/081884再公表公報 [Patent Document 7]: WO2009/081884 re-publication bulletin
根據使用該等蝕刻液或蝕刻劑的洗淨製程，係可不腐蝕金屬配線等選擇性地蝕刻鈦或鎢，而於半導體基板的洗淨製程使用該等蝕刻液或蝕刻劑。 According to the cleaning process using the etching liquid or the etchant, titanium or tungsten can be selectively etched without etching metal wiring or the like, and the etching liquid or the etchant is used in the cleaning process of the semiconductor substrate.
然而，若於具有鈦系金屬與相對於該鈦系金屬為大體積的金屬銅或銅合金之半導體基板使用該等蝕刻劑時，已知由於金屬銅或銅合金對鈦而言為大體積，源自金屬銅或銅合金之銅(氧化銅)的溶出量太多，所溶出的銅(氧化銅)會引起過氧化氫的分解，導致溶液壽命變短，而有需適當控制蝕刻劑中的過氧化氫的濃度等問題點。基於 如此的背景，期望開發可抑制包含於蝕刻劑中的過氧化氫的分解之蝕刻劑。 However, when such an etchant is used for a semiconductor substrate having a titanium-based metal and a metal copper or a copper alloy which is bulky with respect to the titanium-based metal, it is known that metal copper or a copper alloy is bulky for titanium. Copper (copper oxide) derived from metallic copper or copper alloy has too much elution, and the eluted copper (copper oxide) causes decomposition of hydrogen peroxide, resulting in a shortened solution life, and it is necessary to appropriately control the etchant. Problems such as the concentration of hydrogen peroxide. based on Against such a background, it is desirable to develop an etchant that can suppress decomposition of hydrogen peroxide contained in an etchant.
本發明係有鑑於上述狀況，提供一種在對具有鈦系金屬與金屬銅或銅合金的半導體基板使用的情況下，抑制過氧化氫的分解、溶液壽命長、控制蝕刻劑中過氧化氫的濃度之必要性少之半導體基板上的鈦系金屬用蝕刻劑、使用該蝕刻劑的蝕刻方法以及用於與過氧化氫混合使用的蝕刻劑調製液。 In view of the above circumstances, the present invention provides a method for suppressing decomposition of hydrogen peroxide, long solution life, and controlling concentration of hydrogen peroxide in an etchant when used in a semiconductor substrate having a titanium-based metal and a metallic copper or a copper alloy. An etchant for a titanium-based metal on a semiconductor substrate having a small necessity, an etching method using the etchant, and an etchant preparation liquid used for mixing with hydrogen peroxide.
本發明係由以下的構成所成。 The present invention has been made up of the following constitutions.
(1)一種鈦系金屬用蝕刻劑，其係至少包含下述的(A)、(B)、(C)及(D)的水溶液，為具有鈦系金屬與於該鈦系金屬的上部之金屬銅或銅合金的半導體基板上的鈦系金屬用蝕刻劑；(A)過氧化氫；(B)構造中具有氮原子的膦酸系螫合劑；(C)鹼金屬氫氧化物；(D)具有至少1個羥基及至少3個羧基的有機酸。 (1) An etchant for a titanium-based metal, comprising at least the following aqueous solutions (A), (B), (C), and (D), having a titanium-based metal and an upper portion of the titanium-based metal An etchant for a titanium-based metal on a semiconductor substrate of a metal copper or a copper alloy; (A) hydrogen peroxide; (B) a phosphonic acid-based chelating agent having a nitrogen atom in the structure; (C) an alkali metal hydroxide; An organic acid having at least one hydroxyl group and at least three carboxyl groups.
(2)一種蝕刻方法，其係使用至少包含下述的(A)、(B)、(C)及(D)的水溶液之蝕刻劑，選擇性地蝕刻具有鈦系金屬以及於該鈦系金屬的上部之金屬銅或銅合金的半導體基板上的鈦系金屬之蝕刻方法；(A)過氧化氫；(B)構造中具有氮原子的膦酸系螫合劑； (C)鹼金屬氫氧化物；(D)具有至少1個羥基及至少3個羧基的有機酸。 (2) An etching method for selectively etching a titanium-based metal and using the titanium-based metal using an etchant containing at least the following aqueous solutions (A), (B), (C), and (D) a method of etching a titanium-based metal on a semiconductor copper or copper alloy semiconductor substrate; (A) hydrogen peroxide; (B) a phosphonic acid-based chelating agent having a nitrogen atom in the structure; (C) an alkali metal hydroxide; (D) an organic acid having at least one hydroxyl group and at least three carboxyl groups.
(3)一種蝕刻劑調製液，其係至少包含下述的(B)、(C)及(D)的水溶液，且與包含(A)過氧化氫所成的溶液進行混合者，為用以調製具有鈦系金屬與於該鈦系金屬的上部之金屬銅或銅合金的半導體基板上的鈦系金屬用蝕刻劑之蝕刻劑調製液；(B)構造中具有氮原子的膦酸系螫合劑；(C)鹼金屬氫氧化物；(D)具有至少1個羥基及至少3個羧基的有機酸。 (3) An etchant preparation liquid comprising at least the following aqueous solutions (B), (C) and (D), and mixed with a solution containing (A) hydrogen peroxide; An etchant preparation liquid for an etchant for a titanium-based metal having a titanium-based metal and a metal copper or copper alloy on the upper portion of the titanium-based metal; (B) a phosphonic acid-based chelating agent having a nitrogen atom in the structure (C) an alkali metal hydroxide; (D) an organic acid having at least one hydroxyl group and at least three carboxyl groups.
本發明的蝕刻劑，係於半導體元件的製造製程中，使用於例如具有金屬鈦、鈦-鎢合金等鈦系金屬與於該鈦系金屬的上部之金屬銅或銅合金的半導體基板上的鈦系金屬之蝕刻步驟，於使用於如此的半導體基板時，因會抑制過氧化氫的分解，故可達成蝕刻劑的溶液壽命長、控制蝕刻劑中過氧化氫的濃度之必要性少之效果。 The etchant of the present invention is used in a semiconductor device manufacturing process, for example, on a semiconductor substrate having a titanium-based metal such as a metal titanium or a titanium-tungsten alloy and a metal copper or copper alloy on the upper portion of the titanium-based metal. When the metal substrate is used in such a semiconductor substrate, since decomposition of hydrogen peroxide is suppressed, it is possible to achieve a long solution life of the etchant and a small effect of controlling the concentration of hydrogen peroxide in the etchant.
而且，本發明的蝕刻方法，係可有效地蝕刻具有鈦系金屬與於該鈦系金屬的上部之金屬銅或銅合金的半導體基板上的鈦系金屬之方法，藉由使用本發明的蝕刻劑，因不易引起蝕刻劑中的過氧化氫的濃度變化，故蝕刻速度(etching rate)安定，進而達成所謂可安定地得到所期望的量之鈦系金屬被蝕刻的半導體基板之效果。 Further, the etching method of the present invention is a method for efficiently etching a titanium-based metal having a titanium-based metal and a metal copper or copper alloy on the upper portion of the titanium-based metal, by using the etchant of the present invention. Since the concentration of hydrogen peroxide in the etchant is not easily changed, the etching rate is stabilized, and an effect is obtained in which a semiconductor substrate in which a desired amount of titanium-based metal is stably obtained is obtained.
再者，本發明的蝕刻劑調製液，係可藉由混 合過氧化氫而成為本發明的蝕刻劑者，例如使用本發明的蝕刻劑時，係藉由臨用時調製過氧化氫與上述的蝕刻劑調製液，以進一步抑制過氧化氫的分解，達成所謂可更延長蝕刻劑的溶液壽命之效果。 Furthermore, the etchant preparation liquid of the present invention can be mixed by When the etchant of the present invention is used in combination with hydrogen peroxide, for example, when the etchant of the present invention is used, hydrogen peroxide and the etchant preparation liquid described above are prepared to further suppress decomposition of hydrogen peroxide. The effect of extending the life of the solution of the etchant can be further extended.
本發明人等為了達成上述目的，反覆專心研究，結果發現於傳統習知的銅抗蝕劑中，藉由使用具有至少1個羥基及至少3個羧基的有機酸，最能減少源自金屬銅或銅合金之銅(氧化銅)的溶出，又發現於各種螫合劑中，藉由使用構造中具有氮原子的膦酸系螫合劑螫合從金屬銅或銅合金溶出的銅，更具體地螫合氧化銅，可抑制銅(氧化銅)所致之過氧化氫的分解。亦即，藉由組合構造中具有氮原子的膦酸系螫合劑以及具有至少1個羥基及至少3個羧基的有機酸，可抑制源自金屬銅或銅合金之銅(氧化銅)的溶出，例如即使溶出銅(氧化銅)，亦可藉由螫合銅(氧化銅)而減少對過氧化氫的不良影響。因可藉由如此的機制抑制過氧化氫的分解，故發現可安定地蝕刻具有鈦系金屬與金屬銅或銅合金的半導體基板上的鈦系金屬，遂完成本發明。 In order to achieve the above object, the present inventors have repeatedly studied intensively, and as a result, it has been found that in a conventional copper resist, the use of an organic acid having at least one hydroxyl group and at least three carboxyl groups is most effective in reducing copper metal origin. Or the dissolution of copper (copper oxide) of copper alloy, which is found in various chelating agents, and copper which is eluted from metallic copper or copper alloy by using a phosphonic acid chelating agent having a nitrogen atom in the structure, more specifically 螫Copper oxide can inhibit the decomposition of hydrogen peroxide caused by copper (copper oxide). That is, by combining a phosphonic acid chelating agent having a nitrogen atom in the structure and an organic acid having at least one hydroxyl group and at least three carboxyl groups, elution of copper (copper oxide) derived from metallic copper or a copper alloy can be suppressed. For example, even if copper (copper oxide) is eluted, the adverse effect on hydrogen peroxide can be reduced by twisting copper (copper oxide). Since the decomposition of hydrogen peroxide can be suppressed by such a mechanism, it has been found that the titanium-based metal on the semiconductor substrate having the titanium-based metal and the metallic copper or copper alloy can be stably etched, and the present invention has been completed.
於本發明，所謂鈦系金屬(Ti系金屬)，係指Ti或鈦-鎢合金(TiW合金)等以Ti為主成分之金屬。 In the present invention, the titanium-based metal (Ti-based metal) refers to a metal containing Ti as a main component such as Ti or a titanium-tungsten alloy (TiW alloy).
本發明的鈦系金屬用蝕刻劑 Etching agent for titanium-based metal of the present invention
本發明的蝕刻劑，係至少包含(A)過氧化氫；(B)構造中具有氮原子的膦酸系螫合劑；(C)鹼金屬氫氧化物；以及(D)具有至少1個羥基及至少3個羧基的有機酸之水溶液。 The etchant of the present invention comprises at least (A) hydrogen peroxide; (B) a phosphonic acid chelating agent having a nitrogen atom in the structure; (C) an alkali metal hydroxide; and (D) having at least one hydroxyl group and An aqueous solution of at least 3 carboxyl organic acids.
(A)過氧化氫，係在氧化Ti系金屬、容易地進行藉由鹼金屬氫氧化物之Ti系金屬的溶解之目的下使用，可舉例如市售的過氧化氫水等。更具體而言，可使用例如將市售的35%或60%過氧化氫水以例如蒸餾水、去離子水等精製水、超純水等稀釋為後述的濃度之過氧化氫。 (A) Hydrogen peroxide is used for the purpose of oxidizing a Ti-based metal and easily dissolving a Ti-based metal by an alkali metal hydroxide, and commercially available hydrogen peroxide water or the like is exemplified. More specifically, for example, commercially available 35% or 60% hydrogen peroxide water can be diluted with purified water such as distilled water or deionized water, ultrapure water or the like to a concentration of hydrogen peroxide described later.
(B)構造中具有氮原子的膦酸系螫合劑，係於下述目的下使用：配位於經氧化的Ti系金屬，形成水溶性錯合物，容易地進行Ti系金屬的溶解，同時藉由螫合從金屬銅或銅合金溶出的銅，更具體地係螫合氧化銅，而抑制銅(氧化銅)所致之過氧化氫的分解。作為如此的膦酸系螫合劑，可舉例如下述通式[1]或[2]所示者。 (B) A phosphonic acid-based chelating agent having a nitrogen atom in the structure is used for the purpose of: arranging the oxidized Ti-based metal to form a water-soluble complex, and easily dissolving the Ti-based metal while borrowing Copper which is eluted from metallic copper or a copper alloy, more specifically copper oxide, inhibits decomposition of hydrogen peroxide by copper (copper oxide). As such a phosphonic acid chelating agent, the following general formula [1] or [2] is mentioned, for example.
(式中，Q表示氫原子或-R2-PO3H2所示的基，R1及R2分別獨立地表示伸烷基，Y表示氫原子、-R2-PO3H2所示的基或下述通式[3]所示的基，m表示0或1。但是Y為下述通式[3]所示的基時，m為1) (wherein Q represents a hydrogen atom or a group represented by -R 2 -PO 3 H 2 , and R 1 and R 2 each independently represent an alkylene group, and Y represents a hydrogen atom, and -R 2 -PO 3 H 2 represents Or a group represented by the following formula [3], m represents 0 or 1. However, when Y is a group represented by the following formula [3], m is 1)
(式中，Q及R2係與上述相同) (wherein Q and R 2 are the same as above)
(式中，R3及R4分別獨立地表示碳數1至4的伸烷基，n表示1至4的整數，Z1至Z4與n個Z5中至少4個為具有膦酸基的烷基，其餘表示烷基)。 (wherein R 3 and R 4 each independently represent an alkylene group having 1 to 4 carbon atoms, n represents an integer of 1 to 4, and at least 4 of Z 1 to Z 4 and n Z 5 have a phosphonic acid group; The alkyl group, the rest represents an alkyl group).
作為通式[1]之R1所示的伸烷基，可舉出碳數1至12的直鏈狀或分枝狀者，具體而言，例如：亞甲基、伸乙基、伸丙基、三亞甲基、乙基亞甲基、四亞甲基、2-甲基伸丙基、2-甲基三亞甲基、乙基伸乙基、五亞甲基、2,2-二甲基三亞甲基、2-乙基三亞甲基、六亞甲基、七亞甲基、八亞甲基、2-乙基六亞甲基、九亞甲基、十亞甲基、十一亞甲基、十二亞甲基等，其中以例如亞甲基、伸乙基、伸丙基、三亞甲基、乙基亞甲基、四亞甲基、2-甲基伸丙基、2-甲基三亞甲基、乙基伸乙基、五亞甲基、2,2-二甲基三亞甲基、2-乙基三亞甲基、六亞甲基等碳數1至6的直鏈狀或分枝狀的伸烷基較理想，其中以碳數2的伸烷基之伸乙基更理想。 Examples of the alkylene group represented by R 1 of the general formula [1] include a linear or branched carbon number of 1 to 12, and specifically, for example, a methylene group, an ethyl group, and a propylene group. Base, trimethylene, ethylmethylene, tetramethylene, 2-methylpropyl, 2-methyltrimethylene, ethylethyl, pentamethylene, 2,2-dimethyl Trimethylene, 2-ethyltrimethylene, hexamethylene, heptamethylene, octamethylene, 2-ethylhexamethylene, hexamethylene, decamethylene, eleven a group, a dodecamethylene group, etc., wherein, for example, a methylene group, an ethyl group, a propyl group, a trimethylene group, an ethylmethylene group, a tetramethylene group, a 2-methyl propyl group, a 2-methyl group a linear or branched carbon number of 1 to 6 such as a methylene group, an ethylexyl group, a pentamethylene group, a 2,2-dimethyltrimethylene group, a 2-ethyltrimethylene group, or a hexamethylene group. A branched alkyl group is preferred, and an ethyl group having a carbon number of 2 alkyl groups is more desirable.
作為通式[1]及[3]之R2所示的伸烷基，可舉出碳數1至10的直鏈狀或分枝狀者，具體而言，例如：亞甲基、伸乙基、伸丙基、三亞甲基、乙基亞甲基、四亞甲基、2-甲基伸丙基、2-甲基三亞甲基、乙基伸乙基、五亞甲基、2,2-二甲基三亞甲基、2-乙基三亞甲基、六亞甲基、 七亞甲基、八亞甲基、2-乙基六亞甲基、九亞甲基、十亞甲基等，其中以碳數1至2的伸烷基之亞甲基、伸乙基較理想，其中以碳數1的伸烷基之亞甲基更理想。 Examples of the alkylene group represented by R 2 of the general formulae [1] and [3] include a linear or branched carbon number of 1 to 10, and specifically, for example, a methylene group and a stretching group Base, propyl, trimethylene, ethylmethylene, tetramethylene, 2-methylpropyl, 2-methyltrimethylene, ethylethyl, pentamethylene, 2,2 - dimethyltrimethylene, 2-ethyltrimethylene, hexamethylene, heptamethylene, octamethylene, 2-ethylhexamethylene, hexamethylene, decamethylene, etc. Among them, a methylene group having an alkyl group having 1 to 2 carbon atoms and an ethyl group are preferred, and a methylene group having a carbon number of 1 alkyl group is more preferable.
作為通式[1]及[3]之Q，更理想為-R2-PO3H2所示的基。 The Q of the general formulae [1] and [3] is more preferably a group represented by -R 2 -PO 3 H 2 .
作為通式[1]之Y，更理想為-R2-PO3H2所示的基或上述通式[3]所示的基，其中特別理想為-R2-PO3H2所示的基。 The Y represented by the formula [1] is more preferably a group represented by -R 2 -PO 3 H 2 or a group represented by the above formula [3], and particularly preferably represented by -R 2 -PO 3 H 2 Base.
作為通式[1]之m，通常為0或1，較理想為0。再者，m為0時，係指通式[1]之R1所示的基不存在，Y所示的基與氮原子直接鍵結。 As m of the general formula [1], it is usually 0 or 1, and more preferably 0. Further, when m is 0, it means that the group represented by R 1 of the general formula [1] does not exist, and the group represented by Y is directly bonded to the nitrogen atom.
作為通式[2]之R3及R4所示的碳數1至4的伸烷基，可舉出直鏈狀或分枝狀者，具體而言，例如：亞甲基、伸乙基、伸丙基、三亞甲基、乙基亞甲基、四亞甲基、2-甲基伸丙基、2-甲基三亞甲基、乙基伸乙基等，其中以碳數2的伸烷基之伸乙基更理想。 Examples of the alkylene group having 1 to 4 carbon atoms represented by R 3 and R 4 in the general formula [2] include a linear or branched form, and specifically, for example, a methylene group and an ethylidene group. , propyl, trimethylene, ethylmethylene, tetramethylene, 2-methylpropyl, 2-methyltrimethylene, ethylethyl, etc. The base ethyl group is more ideal.
作為通式[2]之n，通常為1至4的整數，較理想為1至2的整數，更理想為1。 n as the general formula [2] is usually an integer of 1 to 4, more preferably an integer of 1 to 2, more preferably 1.
作為通式[2]之Z1至Z5所示的烷基及「具有膦酸基的烷基」之烷基，可舉出碳數1至4的直鏈狀或分枝狀者，具體而言，例如：甲基、乙基、n-丙基、異丙基、n-丁基、異丁基、s-丁基、t-丁基等，其中以碳數1的烷基之甲基較理想。再者，於上述具體例，n-表示正(normal)體，s-表示二級(sec-)體，t-表示三級(tert-)體。 Examples of the alkyl group represented by the formula (2), the alkyl group represented by Z 1 to Z 5 and the "alkyl group having a phosphonic acid group" may be a linear or branched carbon number of 1 to 4, specifically For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group, etc., wherein the alkyl group having a carbon number of 1 The base is ideal. Furthermore, in the above specific examples, n- represents a normal body, s- represents a secondary (sec-) body, and t- represents a tertiary (tert-) body.
作為通式[2]之Z1至Z5所示的「具有膦酸基的烷基」之膦酸基的數目，通常為1至2個，較理想為1個。 The number of the phosphonic acid groups of the "alkyl group having a phosphonic acid group" represented by Z 1 to Z 5 in the general formula [2] is usually 1 to 2, more preferably one.
作為通式[2]之Z1至Z5所示的具有膦酸基的烷基，可舉出碳數1至4的直鏈狀或分枝狀之具有1個或2個膦酸基的烷基，具體而言，例如：單膦醯甲基、單膦醯乙基、單膦醯-n-丙基、單膦醯異丙基、單膦醯-n-丁基、單膦醯異丁基、單膦醯-s-丁基、單膦醯-t-丁基、二膦醯甲基、二膦醯乙基、二膦醯-n-丙基、二膦醯異丙基、二膦醯-n-丁基、二膦醯異丁基、二膦醯-s-丁基、二膦醯-t-丁基等，其中以碳數1至2之具有1個膦酸基的烷基之單膦醯甲基、單膦醯乙基較理想，其中以碳數1之具有1個膦酸基的烷基之單膦醯甲基更理想。再者，於上述具體例，n-表示正(normal)體，s-表示二級(sec-)體，t-表示三級(tert-)體。 Examples of the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 in the general formula [2] include a linear or branched carbon number of 1 to 4 having one or two phosphonic acid groups. Alkyl, specifically, for example, monophosphonium methyl, monophosphonium ethyl, monophosphonium-n-propyl, monophosphonium isopropyl, monophosphonium-n-butyl, monophosphorus Butyl, monophosphonium-s-butyl, monophosphonium-t-butyl, diphosphinium methyl, diphosphinium ethyl, diphosphonium-n-propyl, diphosphonium isopropyl, two Phosphonium-n-butyl, diphosphonium isobutyl, diphosphonium-s-butyl, diphosphonium-t-butyl, etc., wherein the alkyl having one phosphonic acid group has 1 to 2 carbon atoms The monophosphonium methyl group and the monophosphonium ethyl group are preferred, and a monophosphonium methyl group having an alkyl group having one phosphonic acid group of 1 carbon number is more preferable. Furthermore, in the above specific examples, n- represents a normal body, s- represents a secondary (sec-) body, and t- represents a tertiary (tert-) body.
作為通式[2]之Z1至Z5，以Z1至Z4與n個Z5皆為具有膦酸基的烷基為較理想。 As Z 1 to Z 5 of the general formula [2], it is preferred that all of Z 1 to Z 4 and n Z 5 are an alkyl group having a phosphonic acid group.
作為(B)構造中具有氮原子的膦酸系螫合劑的具體例，可舉例如乙基胺基雙(亞甲基膦酸)、十二烷基胺基雙(亞甲基膦酸)、硝基參(亞甲基膦酸)[NTPO]、伸乙基二胺雙(亞甲基膦酸)[EDDPO]、丙烷二胺雙(亞甲基膦酸)[1,2-伸丙基二胺雙(亞甲基膦酸)、1,3-伸丙基二胺雙(亞甲基膦酸)]、伸乙基二胺四(亞甲基膦酸)[EDTPO]、伸乙基二胺四(伸乙基膦酸)、丙烷二胺四亞甲基膦酸[PDTMP][1,2-伸丙基二胺四(亞甲基膦酸)、1,3-伸丙基二胺四(亞甲基膦 酸)]、1,6-六亞甲基二胺四(亞甲基膦酸)等通式[1]所示的膦酸系螫合劑；例如二伸乙基三胺五(亞甲基膦酸)[DEPPO]、二伸乙基三胺五(伸乙基膦酸)、三伸乙基四胺六(亞甲基膦酸)、三伸乙基四胺六(伸乙基膦酸)等通式[2]所示的膦酸系螫合劑等，其中以硝基參(亞甲基膦酸)[NTPO]、伸乙基二胺四(亞甲基膦酸)[EDTPO]、二伸乙基三胺五(亞甲基膦酸)[DEPPO]較理想，其中以硝基參(亞甲基膦酸)[NTPO]、二伸乙基三胺五(亞甲基膦酸)[DEPPO]更理想，又以硝基參(亞甲基膦酸)[NTPO]特別理想。該等較理想的膦酸螫合劑與其他膦酸系螫合劑相比，就所謂過氧化氫的分解抑制效果高之點而言，為較理想的螫合劑。再者，該等膦酸系螫合劑，可單獨使用1種膦酸系螫合劑，亦可使用2種以上的膦酸系螫合劑之組合。而且，該等膦酸系螫合劑，例如亦可使用膦酸的鹼金屬鹽等膦酸鹽、膦酸酯等膦酸衍生物。該等膦酸系螫合劑可使用市售者，亦可使用藉由原本習知的方法適當地合成者，於市售的膦酸系螫合劑，亦有在該膦酸系螫合劑以外包含例如蒸餾水、去離子水等精製水、超純水等水者，而使用包含如此的水之膦酸系螫合劑亦無妨。 Specific examples of the phosphonic acid-based chelating agent having a nitrogen atom in the structure (B) include, for example, ethylamino bis (methylene phosphonic acid), dodecylamino bis (methylene phosphonic acid), Nitrosyl (methylene phosphonic acid) [NTPO], ethyl diamine bis (methylene phosphonic acid) [EDDPO], propane diamine bis (methylene phosphonic acid) [1, 2-propyl propyl Diamine bis (methylene phosphonic acid), 1,3-propylene diamine bis (methylene phosphonic acid), ethylene diamine tetra (methylene phosphonic acid) [EDTPO], ethylene Diamine tetra(extended ethylphosphonic acid), propane diamine tetramethylene phosphonic acid [PDTMP] [1,2-propenyldiamine tetra(methylenephosphonic acid), 1,3-propenyl Amine tetramethylene Phosphonic acid chelating agent represented by the general formula [1] such as acid)], 1,6-hexamethylenediaminetetrakis (methylenephosphonic acid); for example, di-ethyltriamine penta (methylenephosphine) Acid) [DEPPO], di-extension ethyltriamine five (extended ethylphosphonic acid), tri-extended ethyltetramine hexa (methylene phosphonic acid), tri-ethylidene tetraamine (extended ethylphosphonic acid) A phosphonic acid chelating agent represented by the general formula [2], wherein nitrosyl (methylene phosphonic acid) [NTPO], ethylidene diamine tetrakis (methylene phosphonic acid) [EDTPO], Ethyltriamine penta (methylene phosphonic acid) [DEPPO] is preferred, wherein nitrosyl (methylene phosphonic acid) [NTPO], di-ethyltriamine penta (methylene phosphonic acid) [ DEPPO] is more desirable, and is particularly desirable as nitrosyl (methylene phosphonic acid) [NTPO]. Such a preferable phosphonic acid chelating agent is a preferable chelating agent as compared with other phosphonic acid chelating agents insofar as the effect of suppressing decomposition of hydrogen peroxide is high. Further, as the phosphonic acid-based chelating agent, one type of phosphonic acid-based chelating agent may be used alone, or a combination of two or more kinds of phosphonic acid-based chelating agents may be used. Further, as the phosphonic acid-based chelating agent, for example, a phosphonic acid derivative such as a phosphonate or a phosphonate such as an alkali metal salt of a phosphonic acid can be used. These phosphonic acid-based chelating agents may be used commercially, or may be appropriately synthesized by a conventionally known method, and may be, for example, a commercially available phosphonic acid-based chelating agent, or may contain, for example, other than the phosphonic acid-based chelating agent. It is also possible to use a phosphonic acid-based chelating agent containing such water, such as distilled water or deionized water, such as purified water or ultrapure water.
(C)鹼金屬氫氧化物，係在調整/維持本發明的蝕刻劑之pH為所期望的範圍，同時使藉由過氧化氫氧化的Ti系金屬溶解的目的下使用。作為如此的鹼金屬氫氧化物，可舉例如：氫氧化鋰、氫氧化鈉、氫氧化鉀、氫氧化銣、氫氧化銫等，其中以氫氧化鋰、氫氧化鈉、氫氧化鉀較理想，其中以氫氧化鋰、氫氧化鈉更理想。該等較理 想的鹼金屬氫氧化物與其他鹼金屬氫氧化物相比，係不只是對金屬銅或銅合金之Ti系金屬的蝕刻速度高(具有高Ti/Cu的溶解速度比)，在所謂過氧化氫的分解抑制效果高之點為較理想的鹼金屬氫氧化物。再者，該等鹼金屬氫氧化物，可單獨使用1種鹼金屬氫氧化物，亦可使用2種以上的鹼金屬氫氧化物之組合。而且，該等鹼金屬氫氧化物可使用市售者。 (C) The alkali metal hydroxide is used for the purpose of adjusting/maintaining the pH of the etchant of the present invention in a desired range while dissolving the Ti-based metal oxidized by hydrogen peroxide. Examples of such an alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, and barium hydroxide. Among them, lithium hydroxide, sodium hydroxide, and potassium hydroxide are preferred. Among them, lithium hydroxide and sodium hydroxide are more preferable. These are reasonable Compared with other alkali metal hydroxides, the alkali metal hydroxides are not only high in etching rate for Ti-based metals of metallic copper or copper alloys (having a high Ti/Cu dissolution rate ratio), so-called peroxidation. The point where the decomposition inhibition effect of hydrogen is high is a preferable alkali metal hydroxide. Further, as the alkali metal hydroxide, one type of alkali metal hydroxide may be used alone, or a combination of two or more kinds of alkali metal hydroxides may be used. Moreover, such alkali metal hydroxides can be used commercially.
(D)具有至少1個羥基及至少3個羧基的有機酸，係在抑制源自金屬銅或銅合金的銅之溶出的目的下使用。亦即，具有至少1個羥基及至少3個羧基的有機酸，係使用作為銅抗蝕劑。作為如此的具有至少1個羥基及至少3個羧基的有機酸，可舉例如檸檬酸等。再者，該等有機酸，可單獨使用1種有機酸，亦可使用2種以上的有機酸之組合。而且，該等有機酸可使用市售者。 (D) An organic acid having at least one hydroxyl group and at least three carboxyl groups is used for the purpose of suppressing elution of copper derived from metallic copper or a copper alloy. That is, an organic acid having at least one hydroxyl group and at least three carboxyl groups is used as a copper resist. As such an organic acid having at least one hydroxyl group and at least three carboxyl groups, for example, citric acid or the like can be mentioned. Further, as the organic acid, one type of organic acid may be used alone, or a combination of two or more types of organic acids may be used. Moreover, these organic acids can be used by a commercial person.
本發明的蝕刻劑因係水溶液，而為包含水者。作為水，於半導體元件的製造製程中，只要是對半導體基板無不良影響者即無特別限制。水的具體例可舉例如蒸餾水、去離子水等精製水、超純水等，其中以超純水較理想。超純水幾乎不含雜質，於半導體元件的製造製程中，就所謂對半導體基板無不良影響之點而言為較理想的水。 The etchant of the present invention contains water because it is an aqueous solution. The water is not particularly limited as long as it does not adversely affect the semiconductor substrate in the manufacturing process of the semiconductor element. Specific examples of the water include purified water such as distilled water and deionized water, and ultrapure water. Among them, ultrapure water is preferred. Ultrapure water contains almost no impurities, and is ideal for use in a semiconductor device manufacturing process insofar as it does not adversely affect the semiconductor substrate.
於本發明的蝕刻劑中，在構成成分之(A)、(B)、(C)及(D)外，視所需，亦可包含作為其他成分之(E)pH調整劑、(F)界面活性劑等。 In the etchant of the present invention, in addition to the constituent components (A), (B), (C) and (D), (E) pH adjuster, (F) may be contained as other components. Surfactant and the like.
(E)pH調整劑，從可調整/維持本發明的蝕刻 劑的pH為所期望的範圍之觀點等來看，係可適當添加。作為如此的(E)pH調整劑，可舉例如鹽酸、硝酸、硫酸、磷酸、硼酸、氟酸、碳酸等無機酸。再者，該等pH調整劑，可單獨使用1種pH調整劑，亦可使用2種以上的pH調整劑之組合。而且，該等pH調整劑可使用市售者。 (E) pH adjuster from which the etching of the present invention can be adjusted/maintained The pH of the agent can be appropriately added from the viewpoint of a desired range and the like. Examples of such (E) pH adjusters include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, boric acid, hydrofluoric acid, and carbonic acid. Further, as the pH adjuster, one type of pH adjuster may be used alone, or a combination of two or more kinds of pH adjusters may be used. Moreover, these pH adjusters can be used by a commercially available person.
(F)界面活性劑，從可改善本發明的蝕刻劑對半導體基板表面之潤濕性之觀點等來看，係可適當添加。作為如此的(F)界面活性劑，例如陽離子性界面活性劑、陰離子性界面活性劑、非離子性界面活性劑、兩性界面活性劑等。作為陽離子性界面活性劑的具體例，可舉例如：氯化單硬脂基銨、氯化二硬脂基銨、氯化三硬脂基銨等1級至3級的烷基胺鹽；例如聚乙烯多胺等改性脂肪族多胺等。作為陰離子性界面活性劑的具體例，可舉例如：烷基羧酸鈉鹽、烷基羧酸鉀鹽、烷基羧酸銨鹽、烷基苯羧酸鈉鹽、烷基苯羧酸鉀鹽、烷基苯羧酸銨鹽、聚環氧烷烷基醚羧酸鈉鹽、聚環氧烷烷基醚羧酸鉀鹽、聚環氧烷烷基醚羧酸銨鹽、N-醯基肌胺酸鈉鹽、N-醯基肌胺酸鉀鹽、N-醯基肌胺酸銨鹽、N-醯基麩胺酸鈉鹽、N-醯基麩胺酸鉀鹽、N-醯基麩胺酸銨鹽等分子內具有羧基的陰離子性界面活性劑；例如烷基磺酸鈉鹽、烷基磺酸鉀鹽、烷基磺酸銨鹽、例如十二烷基苯磺酸等烷基苯磺酸、例如十二烷基苯磺酸鈉等烷基苯磺酸鈉鹽、例如十二烷基苯磺酸鉀等烷基苯磺酸鉀鹽、例如十二烷基苯磺酸銨等烷基苯磺酸銨鹽、烷基萘磺酸鈉鹽、烷基萘磺酸鉀鹽、烷基萘磺酸銨鹽、聚環氧 烷烷基醚磺酸鈉鹽、聚環氧烷烷基醚磺酸鉀鹽、聚環氧烷烷基醚磺酸銨鹽、N-甲基-N-醯基牛磺酸鈉鹽、N-甲基-N-醯基牛磺酸鉀鹽、N-甲基-N-醯基牛磺酸銨鹽、例如二辛基磺基琥珀酸鈉等二烷基磺基琥珀酸鈉鹽、例如二辛基磺基琥珀酸鉀等二烷基磺基琥珀酸鉀鹽、例如二辛基磺基琥珀酸銨等二烷基磺基琥珀酸銨鹽等分子中具有磺酸基之陰離子性界面活性劑；例如月桂基硫酸鈉等烷基硫酸鈉鹽、例如月桂基硫酸鉀等烷基硫酸鉀鹽、例如月桂基硫酸銨等烷基硫酸銨鹽等分子中具有硫酸酯基的陰離子性界面活性劑；例如烷基膦酸鈉鹽、烷基膦酸鉀鹽、烷基膦酸銨鹽、烷基苯膦酸鈉鹽、烷基苯膦酸鉀鹽、烷基苯膦酸銨鹽、聚環氧烷烷基醚膦酸鈉鹽、聚環氧烷烷基醚膦酸鉀鹽、聚環氧烷烷基醚膦酸銨鹽等分子內具有膦酸基的陰離子性界面活性劑等。作為非離子性界面活性劑的具體例，可舉例如：聚環氧乙烷硬脂基醚等聚環氧乙烷烷基醚、例如聚環氧乙烷油基醚等聚環氧乙烷烯基醚、例如聚環氧乙烷壬基苯基醚等聚環氧烷烷基苯基醚、例如聚環氧丙烷聚環氧乙烷二醇等聚環氧烷二醇、例如聚環氧乙烷單硬脂酸酯等聚環氧乙烷單烷酸酯、例如雙聚環氧乙烷硬脂基胺等雙聚環氧乙烷烷基胺、例如雙聚環氧乙烷硬脂基醯胺等雙聚環氧乙烷烷基醯胺、例如氧化N,N-二甲基烷基胺等氧化烷基胺等。作為兩性界面活性劑的具體例，可舉例如烷基-N,N-二甲基胺基乙酸甜菜鹼、烷基-N,N-二羥基乙基胺基乙酸甜菜鹼等羧基甜菜鹼；例如烷基-N,N-二甲基磺基乙烯銨甜菜鹼等磺 基甜菜鹼；例如2-烷基-N-羧基甲基-N-羥基乙基咪唑鎓甜菜鹼等咪唑鎓甜菜鹼等。再者，該等界面活性劑，可單獨使用1種界面活性劑，亦可使用2種以上的界面活性劑之組合。而且，該等界面活性劑可使用市售者。 (F) The surfactant can be appropriately added from the viewpoint of improving the wettability of the etchant of the present invention on the surface of the semiconductor substrate. As such (F) surfactant, for example, a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, or the like. Specific examples of the cationic surfactant include, for example, a 1 to 3 alkylamine salt such as monostearyl ammonium chloride, distearyl ammonium chloride or tristearic acid chloride; Modified aliphatic polyamines such as polyethylene polyamine. Specific examples of the anionic surfactant include sodium alkyl carboxylate, potassium alkyl carboxylate, ammonium alkyl carboxylate, sodium alkylbenzenecarboxylate, and potassium alkylbenzenecarboxylate. , alkylbenzene carboxylic acid ammonium salt, polyalkylene oxide alkyl ether carboxylate sodium salt, polyalkylene oxide alkyl ether carboxylate potassium salt, polyalkylene oxide alkyl ether carboxylate ammonium salt, N-barium based muscle Sodium aminate, potassium N-methyl sarcosinate, ammonium N-methyl sarcosinate, sodium N-mercapto glutamate, potassium N-mercapto glutamate, N-bismuth bran An anionic surfactant having a carboxyl group in a molecule such as an ammonium amide salt; for example, an alkyl sulfonate sodium salt, an alkyl sulfonate potassium salt, an alkyl sulfonate ammonium salt, an alkylbenzene such as dodecylbenzenesulfonic acid a sulfonic acid, for example, a sodium alkylbenzenesulfonate such as sodium dodecylbenzenesulfonate, an alkylbenzenesulfonate such as potassium dodecylbenzenesulfonate, or an alkane such as ammonium dodecylbenzenesulfonate Ammonium benzenesulfonate, sodium alkylnaphthalenesulfonate, potassium alkylnaphthalenesulfonate, ammonium alkylnaphthalenesulfonate, polyepoxy Alkyl ether sulfonate sodium salt, polyalkylene oxide alkyl ether sulfonate potassium salt, polyalkylene oxide alkyl ether sulfonate ammonium salt, N-methyl-N-mercapto taurine sodium salt, N- a methyl-N-mercapto taurine potassium salt, an N-methyl-N-mercapto taurine ammonium salt, a dialkyl sulfosuccinate sodium salt such as sodium dioctyl sulfosuccinate, for example, two An anionic surfactant having a sulfonic acid group in a molecule such as a potassium dialkyl sulfosuccinate such as potassium octyl sulfosuccinate or an ammonium salt of a dialkyl sulfosuccinate such as ammonium dioctylsulfosuccinate An alkylsulfate salt such as sodium lauryl sulfate, an alkylsulfate salt such as potassium lauryl sulfate, or an anionic surfactant having a sulfate group in a molecule such as an ammonium alkyl sulfate such as ammonium lauryl sulfate; For example, alkyl phosphonate sodium salt, alkyl phosphonic acid potassium salt, alkyl phosphonic acid ammonium salt, alkyl phenylphosphonate sodium salt, alkyl phenyl phosphonate potassium salt, alkyl phenyl phosphonate ammonium salt, polyalkylene oxide An anionic surfactant having a phosphonic acid group in a molecule such as an alkyl ether phosphonate sodium salt, a polyalkylene oxide alkyl ether phosphonate potassium salt or a polyalkylene oxide alkyl ether phosphonate ammonium salt. Specific examples of the nonionic surfactant include polyethylene oxide alkyl ethers such as polyethylene oxide stearyl ether, and polyethylene oxide olefins such as polyethylene oxide oleyl ether. a polyether alkylene oxide such as polyethylene oxide nonylphenyl ether, a polyalkylene oxide glycol such as polypropylene oxide polyethylene oxide glycol, such as polyethylene oxide a polyethylene oxide monoalkane such as an alkanomonostearate, a dipolyethylene oxide alkylamine such as a diethylene oxide stearylamine, such as a bis-ethylene oxide stearyl hydrazine; A di-polyethylene oxide alkyl decylamine such as an amine, for example, an oxidized alkylamine such as an N,N-dimethylalkylamine oxide. Specific examples of the amphoteric surfactant include carboxybetaine such as alkyl-N,N-dimethylaminoacetate betaine or alkyl-N,N-dihydroxyethylaminoacetate betaine; Alkyl-N,N-dimethylsulfoethylammonium betaine and the like A betaine; for example, an imidazolium betaine such as 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine or the like. Further, as the surfactant, one type of surfactant may be used alone, or a combination of two or more types of surfactants may be used. Moreover, such surfactants can be used commercially.
本發明的蝕刻劑，從對構成半導體元件的構件等沒有不良影響而可蝕刻Ti系金屬的觀點來看，有期望不包含上述(A)、(B)、(C)及(D)以外的其他成分的情況。再者，所謂「不含其他成分(只含上述(A)、(B)、(C)及(D))」，係指不包含對上述構件等有不良影響之虞的量以上之其他成分。亦即，不意味著排除僅包含微量其他成分，而實質上不包含其他成分。 The etchant of the present invention is desirably not including the above (A), (B), (C), and (D) from the viewpoint of etching the Ti-based metal without adversely affecting the member constituting the semiconductor element or the like. The case of other ingredients. In addition, the phrase "excluding other components (including only the above (A), (B), (C), and (D))" refers to other components that do not contain an amount of enthalpy that adversely affects the above-described members and the like. . That is, it does not mean that only a small amount of other components are excluded, and substantially no other components are included.
本發明的蝕刻劑的(A)過氧化氫、(B)構造中具有氮原子的膦酸系螫合劑、(C)鹼金屬氫氧化物、(D)具有至少1個羥基及至少3個羧基的有機酸、(E)pH調整劑以及(F)界面活性劑，以調整為以下表示的重量%濃度為理想。 (A) hydrogen peroxide of the etchant of the present invention, a phosphonic acid chelating agent having a nitrogen atom in the (B) structure, (C) an alkali metal hydroxide, (D) having at least one hydroxyl group and at least three carboxyl groups The organic acid, the (E) pH adjuster, and the (F) surfactant are preferably adjusted to the weight % concentration shown below.
(A)過氧化氫的重量%濃度，相對於蝕刻劑的總重量之(A)的重量%通常為10至33重量%，較理想為10至30重量%。於(A)的重量%濃度未達10重量%時，有導致Ti系金屬的蝕刻速度變得極慢之虞。於(A)的重量%濃度超過33重量%時，從金屬銅或銅合金溶出的銅(氧化銅)會使過氧化氫分解，有發生過氧化氫的分解所致之異常發熱之虞。 (A) The weight % concentration of hydrogen peroxide is usually 10 to 33% by weight, and more desirably 10 to 30% by weight, based on the total weight of the etchant (A). When the weight % concentration of (A) is less than 10% by weight, the etching rate of the Ti-based metal becomes extremely slow. When the weight % concentration of (A) exceeds 33% by weight, copper (copper oxide) eluted from metallic copper or a copper alloy decomposes hydrogen peroxide, and there is a possibility of abnormal heat generation due to decomposition of hydrogen peroxide.
(B)構造中具有氮原子的膦酸系螫合劑的重 量%濃度，相對於蝕刻劑的總重量之(B)的重量%通常為0.05至5重量%，較理想為0.05至3重量%，更理想為0.1至3重量%。於(B)的重量%濃度未達0.05重量%時，無法補充(螫合)從金屬銅或銅合金溶出的銅(氧化銅)，因沒有被補充(螫合)的銅(氧化銅)使過氧化氫分解，而有發生過氧化氫的分解所致之異常發熱之虞。於(B)的重量%濃度超過5重量%時，蝕刻對象之Ti系金屬的選擇性有降低之虞。 (B) The weight of the phosphonic acid chelating agent having a nitrogen atom in the structure The % by weight, based on the total weight of the etchant (B), is usually from 0.05 to 5% by weight, more preferably from 0.05 to 3% by weight, still more preferably from 0.1 to 3% by weight. When the concentration by weight of (B) is less than 0.05% by weight, copper (copper oxide) eluted from metallic copper or copper alloy cannot be replenished (copper) without copper (copper oxide) Hydrogen peroxide decomposes, and there is an abnormal heat generation caused by decomposition of hydrogen peroxide. When the weight % concentration of (B) exceeds 5% by weight, the selectivity of the Ti-based metal to be etched is lowered.
(C)鹼金屬氫氧化物的重量%濃度，相對於蝕刻劑的總重量之(C)的重量%通常為0.2至5重量%，較理想為0.2至4重量%，更理想為0.3至4重量%。於(C)的重量%濃度未達0.2重量%時，Ti系金屬的蝕刻速度有降低之虞。於(C)的重量濃度%超過5重量%時，有引起過氧化氫的自行分解，發生因過氧化氫的自行分解所致之異常發熱之虞。 (C) The weight % concentration of the alkali metal hydroxide is usually 0.2 to 5% by weight, more preferably 0.2 to 4% by weight, still more preferably 0.3 to 4% by weight based on the total weight of the etchant (C). weight%. When the weight % concentration of (C) is less than 0.2% by weight, the etching rate of the Ti-based metal is lowered. When the weight concentration % of (C) exceeds 5% by weight, self-decomposition of hydrogen peroxide occurs, and abnormal heat generation due to self-decomposition of hydrogen peroxide occurs.
(D)具有至少1個羥基及至少3個羧基的有機酸的重量%濃度，相對於蝕刻劑的總重量之(D)的重量%通常為0.01至5重量%，較理想為0.03至3重量%，更理想為0.04至1重量%。於(D)的重量%濃度未達0.01重量%時，有銅容易從金屬銅或銅合金溶出之虞。於(D)的重量%濃度超過5重量%時，蝕刻對象之Ti系金屬的選擇性有降低之虞。 (D) The weight % concentration of the organic acid having at least one hydroxyl group and at least 3 carboxyl groups, and the weight % of (D) based on the total weight of the etchant is usually 0.01 to 5% by weight, more preferably 0.03 to 3 parts by weight. %, more desirably 0.04 to 1% by weight. When the weight % concentration of (D) is less than 0.01% by weight, there is a possibility that copper is easily eluted from metallic copper or a copper alloy. When the concentration by weight of (D) exceeds 5% by weight, the selectivity of the Ti-based metal to be etched is lowered.
(E)pH調整劑的重量%濃度，相對於蝕刻劑的總重量之(E)的重量%通常為0.05至4重量%，較理想為0.2至3重量%。於(E)的重量%濃度超過4重量%時，Ti系金屬 的蝕刻速度有降低之虞。 (E) The weight % concentration of the pH adjuster is usually from 0.05 to 4% by weight, more preferably from 0.2 to 3% by weight, based on the total weight of the etchant (E). Ti-based metal when the concentration by weight of (E) exceeds 4% by weight The etch rate is reduced.
(F)界面活性劑的重量%濃度，相對於蝕刻劑的總重量之(F)的重量%通常為0.001至1重量%，較理想為0.01至0.5重量%。於(F)的重量%濃度超過1重量%時，Ti系金屬的蝕刻速度恐會降低。 The weight % of the (F) surfactant is usually 0.001 to 1% by weight, and more preferably 0.01 to 0.5% by weight, based on the total weight of the etchant. When the weight % concentration of (F) exceeds 1% by weight, the etching rate of the Ti-based metal may be lowered.
本發明的蝕刻劑，係中性至鹼性的水溶液，其中以具有7以上10以下的pH之水溶液較理想，其中以具有7.5以上9.5以下的pH之水溶液更理想，以具有超過8.0、9.5以下的pH之水溶液特別理想。於水溶液的pH未達7時，恐有Ti系金屬的蝕刻速度降低、(B)構造中具有氮原子的膦酸系螫合劑的錯合物形成能力降低、或蝕刻對象之Ti系金屬的選擇性降低之虞。於水溶液的pH超過10時，因過氧化氫的安定性低，引起過氧化氫的自行分解，恐有產生過氧化氫的自行分解所致之異常發熱、蝕刻對象之Ti系金屬的選擇性降低、或腐蝕後述的矽(Si)基板等半導體構件之虞。而且，本發明的蝕刻劑係調整pH為如此的較理想的範圍，藉此使蝕刻劑的蝕刻速度可為所期望的速度，金屬銅或銅合金幾乎不會被蝕刻，而可安定地得到只有Ti系金屬被蝕刻的半導體基板。再者，pH的調整，主要可藉由調整(C)鹼金屬氫氧化物的含量進行。 The etchant of the present invention is a neutral to alkaline aqueous solution, and an aqueous solution having a pH of 7 or more and 10 or less is preferable, and an aqueous solution having a pH of 7.5 or more and 9.5 or less is more preferable, and it is more than 8.0 and 9.5 or less. An aqueous solution of pH is particularly desirable. When the pH of the aqueous solution is less than 7, the etching rate of the Ti-based metal may be lowered, and the complex formation ability of the phosphonic acid-based chelating agent having a nitrogen atom in the (B) structure may be lowered, or the selection of the Ti-based metal to be etched may be selected. The reduction in sexuality. When the pH of the aqueous solution exceeds 10, the stability of hydrogen peroxide is low, and hydrogen peroxide is decomposed by itself, and abnormal heat generation due to self-decomposition of hydrogen peroxide may occur, and selectivity of Ti-based metal to be etched may be lowered. Or etching a semiconductor member such as a germanium (Si) substrate described later. Moreover, the etchant of the present invention adjusts the pH to such a desirable range, whereby the etching rate of the etchant can be a desired speed, and the metallic copper or copper alloy is hardly etched, and can be stably obtained only A semiconductor substrate in which a Ti-based metal is etched. Further, the pH adjustment can be mainly carried out by adjusting the content of (C) alkali metal hydroxide.
本發明的蝕刻劑之pH，係於不稀釋下根據JIS Z8802-1984，使用市售的pH計進行測定。 The pH of the etchant of the present invention is measured without using a commercially available pH meter according to JIS Z8802-1984 without dilution.
本發明的蝕刻劑的調製方法，只要是可調製包含(A)過氧化氫、(B)構造中具有氮原子的膦酸系螫合 劑、(C)鹼金屬氫氧化物及(D)具有至少1個羥基及至少3個羧基的有機酸，以及視所需之(E)pH調整劑及(F)界面活性劑之方法，調製方法本身無特別限制。作為調製方法的具體例，可舉例如：於超純水中添加(B)構造中具有氮原子的膦酸系螫合劑、(C)鹼金屬氫氧化物、(D)具有至少1個羥基及至少3個羧基的有機酸後，視所需添加(F)界面活性劑，再視所需添加(E)pH調整劑，調整pH後，攪拌成為均勻的水溶液之方法等。如此調製的本發明的蝕刻劑，可於使用前進行過濾處理等。 The method for preparing an etchant according to the present invention is to prepare a phosphonic acid-based compound having (A) hydrogen peroxide and a nitrogen atom in the (B) structure. a compound, (C) an alkali metal hydroxide, and (D) an organic acid having at least one hydroxyl group and at least three carboxyl groups, and a method of preparing (E) a pH adjuster and (F) a surfactant, The method itself is not particularly limited. Specific examples of the preparation method include a phosphonic acid-based chelating agent having a nitrogen atom in the (B) structure, (C) an alkali metal hydroxide, and (D) having at least one hydroxyl group in (B) ultrapure water. After the organic acid of at least three carboxyl groups, a surfactant (F) is added as needed, and (E) a pH adjuster is added as needed, and the pH is adjusted, and the mixture is stirred into a uniform aqueous solution. The etchant of the present invention thus prepared can be subjected to a filtration treatment or the like before use.
作為調製本發明的蝕刻劑時所使用的攪拌/混合裝置，可舉例如攪拌機、分散機等。作為攪拌機，可舉例如機械攪拌器、磁性攪拌器等。而且，作為分散機，可舉例如均質機、超音波分散機、球磨機、珠磨機等。 The stirring/mixing device used in the preparation of the etchant of the present invention may, for example, be a stirrer or a disperser. As a stirrer, a mechanical stirrer, a magnetic stirrer, etc. are mentioned, for example. Further, examples of the dispersing machine include a homogenizer, an ultrasonic disperser, a ball mill, and a bead mill.
本發明的蝕刻方法 Etching method of the present invention
本發明的蝕刻方法，其特徵為使用至少包含(A)過氧化氫、(B)構造中具有氮原子的膦酸系螫合劑、(C)鹼金屬氫氧化物、(D)具有至少1個羥基及至少3個羧基的有機酸的水溶液之蝕刻劑，進行選擇性地蝕刻具有鈦系金屬以及於該鈦系金屬的上部之金屬銅或銅合金的半導體基板上的鈦系金屬。亦即，本發明的蝕刻方法，其特徵為使用本發明的蝕刻劑，蝕刻方法本身無特別限制。 The etching method of the present invention is characterized by using at least one of (A) hydrogen peroxide, a phosphonic acid chelating agent having a nitrogen atom in the (B) structure, (C) an alkali metal hydroxide, and (D) An etchant of an aqueous solution of a hydroxyl group and an organic acid of at least three carboxyl groups selectively etches a titanium-based metal having a titanium-based metal and a metal substrate of a metal copper or a copper alloy on the upper portion of the titanium-based metal. That is, the etching method of the present invention is characterized in that the etching method of the present invention is used, and the etching method itself is not particularly limited.
作為本發明的蝕刻方法之具體例，首先，先藉由上述調製方法，準備調製為既定的濃度範圍之本發明的蝕刻劑。然後，例如於本發明的蝕刻劑浸漬具有Ti系金 屬以及於該Ti系金屬的上部之金屬銅或銅合金的半導體基板，藉此可選擇性地蝕刻Ti系金屬。再者，蝕刻的模式並不限於浸漬式，亦可可適當採用浸漬式外之一邊旋轉半導體基板一邊滴下本發明的蝕刻劑之旋轉(滴下)式、噴霧本發明的蝕刻劑之噴霧(spray)式等通常於本領域採行的模式。 As a specific example of the etching method of the present invention, first, an etchant of the present invention prepared to have a predetermined concentration range is prepared by the above-described preparation method. Then, for example, the etchant of the present invention is impregnated with Ti-based gold A semiconductor substrate of a metal copper or a copper alloy on the upper portion of the Ti-based metal can selectively etch the Ti-based metal. Further, the mode of etching is not limited to the immersion type, and a spin type of the etchant of the present invention may be sprayed by appropriately dropping the etchant of the present invention while immersing the outer side of the semiconductor substrate. Such as the pattern usually adopted in the field.
作為本發明的蝕刻方法之半導體基板的處理方式，可採用單片式、批次式的任一種。所謂單片式，一般係指一片一片的處理半導體基板的方法，所謂批次式，一般係指同時處理複數片的半導體基板的方法。 As a processing method of the semiconductor substrate of the etching method of the present invention, either a single chip type or a batch type can be employed. The monolithic type generally refers to a method of processing a semiconductor substrate one by one, and the batch type generally refers to a method of simultaneously processing a plurality of semiconductor substrates.
本發明的蝕刻方法之蝕刻溫度，只要是通常在本領域採行的蝕刻溫度即無特別限制。蝕刻溫度的具體例，例如為10至50℃。 The etching temperature of the etching method of the present invention is not particularly limited as long as it is an etching temperature generally employed in the art. Specific examples of the etching temperature are, for example, 10 to 50 °C.
本發明的蝕刻方法之蝕刻時間，因取決於蝕刻對象之Ti系金屬的形狀、厚度等而無法一概而論，實用上例如通常為30秒至1小時，較理想為1至30分鐘，更理想為1至10分鐘。 The etching time of the etching method of the present invention cannot be generalized depending on the shape and thickness of the Ti-based metal to be etched, and is practically, for example, usually 30 seconds to 1 hour, more preferably 1 to 30 minutes, and still more preferably 1 Up to 10 minutes.
-本發明的蝕刻劑調製液- - Etchant preparation liquid of the present invention -
本發明的蝕刻劑調製液，係至少包含(B)構造中具有氮原子的膦酸系螫合劑、(C)鹼金屬氫氧化物以及(D)具有至少1個羥基及至少3個羧基的有機酸的水溶液，且與包含(A)過氧化氫所成的溶液混合者，為用以調製具有鈦系金屬與於該鈦系金屬的上部之金屬銅或銅合金的半導體基板上的鈦系金屬用蝕刻劑者。 The etchant preparation liquid of the present invention contains at least a phosphonic acid-based chelating agent having a nitrogen atom in the structure (B), (C) an alkali metal hydroxide, and (D) an organic having at least one hydroxyl group and at least three carboxyl groups. An aqueous solution of an acid mixed with a solution containing (A) hydrogen peroxide is a titanium-based metal used to prepare a semiconductor substrate having a titanium-based metal and a metallic copper or copper alloy on the upper portion of the titanium-based metal. Use etchant.
亦即，本發明的蝕刻劑調製液，係與包含(A)過氧化氫所成的溶液混合而用以調製本發明的蝕刻劑者，作為本發明的蝕刻劑的供應型態，係指以2液型供應時包含含(A)過氧化氫所成的溶液以外者之水溶液。 That is, the etchant preparation liquid of the present invention is mixed with a solution containing (A) hydrogen peroxide to prepare the etchant of the present invention, and the supply form of the etchant of the present invention means When the liquid type is supplied, an aqueous solution containing a solution other than (A) hydrogen peroxide is contained.
如所述，本發明的蝕刻劑係以包含(A)過氧化氫所成的溶液以及至少包含(B)構造中具有氮原子的膦酸系螫合劑、(C)鹼金屬氫氧化物以及(D)具有至少1個羥基及至少3個羧基的有機酸的水溶液之蝕刻劑調製液的2液型供應，於使用本發明的蝕刻劑時，混合該等而成為本發明的蝕刻劑，藉此進一步抑制過氧化氫的分解，而可進一步延長蝕刻劑的溶液壽命。因此，本發明的蝕刻劑調製液與包含(A)過氧化氫所成的溶液之混合，係期望在本發明的蝕刻劑臨用之前進行。 As described, the etchant of the present invention is a solution comprising (A) hydrogen peroxide and at least a phosphonic acid chelating agent having a nitrogen atom in (B) configuration, (C) an alkali metal hydroxide and ( D) a two-liquid type supply of an etchant preparation liquid of an aqueous solution of an organic acid having at least one hydroxyl group and at least three carboxyl groups, and when the etchant of the present invention is used, the etchant is mixed as the etchant of the present invention. The decomposition of hydrogen peroxide is further suppressed, and the solution life of the etchant can be further extended. Therefore, the mixing of the etchant preparation liquid of the present invention and the solution containing (A) hydrogen peroxide is desirably carried out before the etchant of the present invention is used.
本發明的蝕刻劑調製液中之(B)構造中具有氮原子的膦酸系螫合劑、(C)鹼金屬氫氧化物以及(D)具有至少1個羥基及至少3個羧基的有機酸的各構成成分的重量%濃度，只要在與包含(A)過氧化氫所成的溶液混合成為本發明的蝕刻劑時，各構成成分(B)、(C)及(D)的重量%濃度可成為上述重量%濃度即無特別限制，例如只要調製包含重量%濃度調整為以下所示的範圍之各成分之蝕刻劑調製液，並將其與包含(A)過氧化氫所成的溶液混合，即可調製本發明的蝕刻劑調製液。 The phosphonic acid-based chelating agent having a nitrogen atom in the (B) structure of the etchant preparation liquid of the present invention, (C) an alkali metal hydroxide, and (D) an organic acid having at least one hydroxyl group and at least three carboxyl groups When the weight % concentration of each component is mixed with the solution containing (A) hydrogen peroxide to form an etchant of the present invention, the weight % concentration of each component (B), (C), and (D) may be The weight % concentration is not particularly limited. For example, an etchant preparation liquid containing a component having a concentration by weight adjusted to the range shown below is prepared, and mixed with a solution containing (A) hydrogen peroxide. The etchant preparation of the present invention can be prepared.
本發明的蝕刻劑調製液中之(B)構造中具有氮原子的膦酸系螫合劑，相對於蝕刻劑調製液的總重量之 (B)的重量%通常為1至10重量%，較理想為1至8重量%，更理想為2至6重量%。 The phosphonic acid-based chelating agent having a nitrogen atom in the (B) structure in the etchant preparation liquid of the present invention, relative to the total weight of the etchant preparation liquid The weight % of (B) is usually from 1 to 10% by weight, more preferably from 1 to 8% by weight, still more preferably from 2 to 6% by weight.
本發明的蝕刻劑調製液中(C)鹼金屬氫氧化物，相對於蝕刻劑調製液的總重量之(C)的重量%通常為4至10重量%，較理想為5至10重量%，更理想為6至10重量%。 The (C) alkali metal hydroxide in the etchant preparation liquid of the present invention is usually from 4 to 10% by weight, preferably from 5 to 10% by weight, based on the total weight of the etchant preparation liquid (C). More preferably, it is 6 to 10% by weight.
本發明的蝕刻劑調製液中(D)具有至少1個羥基及至少3個羧基的有機酸，相對於蝕刻劑調製液的總重量之(D)的重量%通常為0.2至10重量%，較理想為0.2至8重量%，更理想為0.4至6重量%。 In the etchant preparation liquid of the present invention, (D) an organic acid having at least one hydroxyl group and at least three carboxyl groups, and the weight % of (D) based on the total weight of the etchant preparation liquid is usually 0.2 to 10% by weight. It is desirably 0.2 to 8% by weight, more desirably 0.4 to 6% by weight.
本發明的蝕刻劑調製液，除構成成分之(B)、(C)及(D)外，亦可視所需而包含作為其他成分之(E)pH調整劑、(F)界面活性劑等。本發明的蝕刻劑調製液中該等的重量%濃度，只要在與包含(A)過氧化氫所成的溶液混合成為本發明的蝕刻劑時，各成分(E)及(F)的重量%濃度可成為上述重量%濃度即可，無特別限制。 In addition to the constituent components (B), (C) and (D), the etchant preparation liquid of the present invention may contain (E) a pH adjuster, (F) a surfactant, etc. as other components, as needed. The weight % concentration in the etchant preparation liquid of the present invention is the weight % of each component (E) and (F) as long as it is mixed with the solution containing (A) hydrogen peroxide to form the etchant of the present invention. The concentration may be the above-mentioned weight% concentration, and is not particularly limited.
包含調整為如此的重量%濃度之(B)、(C)及(D)以及視所需之(E)及(F)的各成分之蝕刻劑調製液，通常係與20至35重量%、較理想為20至30重量%、更理想為25至30重量%的包含(A)過氧化氫所成的溶液混合。 An etchant preparation liquid containing the components (B), (C), and (D) adjusted to such a weight % concentration, and optionally (E) and (F), usually in an amount of 20 to 35 wt%, More preferably, it is 20 to 30% by weight, more preferably 25 to 30% by weight, of a solution comprising (A) hydrogen peroxide.
包含(A)過氧化氫所成的溶液(第1液)與本發明的蝕刻劑調製液(第2液)的混合比[第1液：第2液]，以重量比為基準，通常為50：50至95：5，較理想為60：40至90：10，更理想為70：30至80：20。 The mixing ratio of the solution (the first liquid) containing (A) hydrogen peroxide and the etchant preparation liquid (the second liquid) of the present invention [the first liquid: the second liquid] is usually based on the weight ratio. 50:50 to 95:5, preferably 60:40 to 90:10, more preferably 70:30 to 80:20.
包含(A)過氧化氫所成的溶液與本發明的蝕刻劑調製液的混合方法，亦即，由包含(A)過氧化氫所成的溶液與本發明的蝕刻劑調製液調製本發明的蝕刻劑之方法，只要適當採用上述調製方法即可，調製時所使用的攪拌/混合裝置，亦可使用上述攪拌/混合裝置。 a method of mixing (A) a solution of hydrogen peroxide with an etchant preparation solution of the present invention, that is, a solution comprising (A) hydrogen peroxide and an etchant preparation of the present invention As the method of the etchant, the above-mentioned preparation method may be suitably employed, and the above-mentioned stirring/mixing device may be used as the stirring/mixing device used in the preparation.
包含(A)過氧化氫所成的溶液與本發明的蝕刻劑調製液的pH並無特別限制，該等溶液混合時的pH，亦即，只要混合該等成為本發明的蝕刻劑時的pH，可成為上述的pH即可。換言之，包含(A)過氧化氫所成的溶液與本發明的蝕刻劑調製液的pH通常為中性至鹼性，較理想係以使本發明的蝕刻劑成為具有7以上10以下，更理想為7.5以上9.5以下，更加理想為超過8.0、9.5以下的pH之方式，調整包含(A)過氧化氫所成的溶液與本發明的蝕刻劑調製液的pH即可。 The pH of the solution containing (A) hydrogen peroxide and the etchant preparation liquid of the present invention is not particularly limited, and the pH at which the solutions are mixed, that is, the pH at which the etchant of the present invention is mixed is used. It can be the above pH. In other words, the pH of the solution containing (A) hydrogen peroxide and the etchant preparation liquid of the present invention is usually neutral to alkaline, and it is preferable that the etchant of the present invention has 7 or more and 10 or less. The pH of the solution containing (A) hydrogen peroxide and the etchant preparation liquid of the present invention may be adjusted so as to be 7.5 or more and 9.5 or less, more preferably more than 8.0 and 9.5 or less.
本發明的蝕刻劑調製液，在保存時、流通時 等未使用時，為了盡可能地使體積小，各構成成分之(B)、(C)及(D)的重量%濃度，例如為上述重量%濃度的10倍至100倍的高濃度，也沒有問題。具有如此之高濃度的成分之本發明的蝕刻劑調製液，可於調製時適當地用水稀釋而使用。 The etchant preparation liquid of the present invention is stored and circulated When it is not used, in order to make the volume as small as possible, the weight % concentration of each of the constituent components (B), (C), and (D) is, for example, a high concentration of 10 times to 100 times the weight % concentration described above. no problem. The etchant preparation liquid of the present invention having such a high concentration of components can be suitably diluted with water at the time of preparation.
關於本發明的半導體基板 About the semiconductor substrate of the present invention
關於本發明的半導體基板，係於構成半導體基板的晶圓的上部至少具有Ti系金屬，又於該Ti系金屬的上部具有金屬銅或銅合金的半導體基板。作為構成半導體基板的 晶圓之具體例，可舉例如：矽(Si)晶圓、碳化矽(SiC)晶圓、含矽之樹脂系晶圓(玻璃環氧晶圓)等矽系材料的晶圓；磷化鎵(GaP)晶圓、砷化鎵(GaAs)晶圓、磷化銦(InP)晶圓等。而且，作為矽(Si)晶圓，亦可為摻雜磷(P)、砷(As)、銻(Sb)等5價原子於矽(Si)晶圓之n型矽(Si)晶圓，摻雜硼(B)、鎵(Ga)等3價原子於矽(Si)晶圓之p型矽(Si)晶圓。再者，作為矽(Si)晶圓的矽(Si)，例如可為非晶矽、單結晶矽、多結晶體矽(multicrystalline silicon)、多晶矽(polysilicon)的任一種。如此的晶圓中，本發明的蝕刻劑及蝕刻方法，適合使用於矽(Si)晶圓、碳化矽(SiC)晶圓、含矽之樹脂系晶圓(玻璃環氧晶圓)等含矽系材料的晶圓。 The semiconductor substrate of the present invention is a semiconductor substrate having at least a Ti-based metal on the upper portion of the wafer constituting the semiconductor substrate and a metal copper or a copper alloy on the upper portion of the Ti-based metal. As a semiconductor substrate Specific examples of the wafer include a wafer of a lanthanum material such as a cerium (Si) wafer, a tantalum carbide (SiC) wafer, or a resin-based wafer (glass epoxy wafer); and gallium phosphide; (GaP) wafers, gallium arsenide (GaAs) wafers, indium phosphide (InP) wafers, etc. Further, as the bismuth (Si) wafer, an n-type germanium (Si) wafer doped with a pentavalent atom such as phosphorus (P), arsenic (As), or antimony (Sb) on a germanium (Si) wafer may be used. A p-type germanium (Si) wafer doped with a trivalent atom such as boron (B) or gallium (Ga) on a germanium (Si) wafer. Further, the bismuth (Si) which is a bismuth (Si) wafer may be, for example, any of amorphous bismuth, single crystal ruthenium, polycrystalline silicon, and polysilicon. In such a wafer, the etchant and the etching method of the present invention are suitable for use in germanium (Si) wafers, tantalum carbide (SiC) wafers, and resin-containing wafers (glass epoxy wafers). Wafer of material.
本發明的半導體基板，亦可於上述晶圓的上部具有絕緣膜。作為該絕緣膜的具體例，可舉例如二氧化矽(SiO2)膜、正矽酸四乙酯(Si(OC2H5)4)膜[TEOS膜]等矽氧化膜，例如氮化矽(Si3N4)、氮化碳化矽(SiNC)等矽氮化膜，例如低介電率(Low-k)膜[SiOC膜、SiC膜]等。 The semiconductor substrate of the present invention may have an insulating film on the upper portion of the wafer. Specific examples of the insulating film include an antimony oxide film such as a cerium oxide (SiO 2 ) film or a tetraethyl orthosilicate (Si(OC 2 H 5 ) 4 ) film [TEOS film], such as tantalum nitride. A germanium nitride film such as (Si 3 N 4 ) or tantalum nitride (SiNC), for example, a low dielectric constant (Low-k) film [SiOC film, SiC film] or the like.
本發明的半導體基板，係至少具有Ti系金屬者，該Ti系金屬可為如上述之僅含金屬Ti者，亦可為含金屬Ti與其他金屬的合金(Ti系合金)。此處，所謂Ti系合金，係指Ti為主成分之合金，可舉例如包含選自鎢(W)、鎳(Ni)、鋁(Al)等之1種以上的金屬與Ti的合金。作為如此的合金之具體例，可舉例如鈦-鎢(TiW合金)、鈦-鎳(TiNi合金)、鈦-鋁(TiAl合金)等。本發明的蝕刻劑及蝕刻方法，適合使用於金屬Ti或鈦-鎢(TiW合金)。 The semiconductor substrate of the present invention has at least a Ti-based metal, and the Ti-based metal may be a metal-containing Ti as described above, or may be an alloy (Ti-based alloy) containing a metal Ti and another metal. Here, the Ti-based alloy is an alloy containing Ti as a main component, and examples thereof include an alloy containing one or more metals selected from the group consisting of tungsten (W), nickel (Ni), and aluminum (Al) and Ti. Specific examples of such an alloy include titanium-tungsten (TiW alloy), titanium-nickel (TiNi alloy), and titanium-aluminum (TiAl alloy). The etchant and etching method of the present invention are suitably used for metal Ti or titanium-tungsten (TiW alloy).
本發明的Ti系金屬，係於本發明的半導體基板中，構成阻隔金屬、密合層等的金屬。 The Ti-based metal of the present invention is a metal which is a barrier metal, an adhesion layer or the like in the semiconductor substrate of the present invention.
本發明的半導體基板係於Ti系金屬的上部具有金屬銅或銅合金者，該金屬銅或銅合金，係構成密合層、配線或凸塊(bump)等的金屬。 The semiconductor substrate of the present invention has a metal copper or a copper alloy on the upper portion of the Ti-based metal, and the metal copper or copper alloy constitutes a metal such as an adhesion layer, a wiring, or a bump.
本發明的金屬銅或銅合金為銅配線或銅合金配線時，此處所謂銅合金配線，係指以銅為主成分的銅合金配線，可舉例如包含選自鎂(Mg)、錳(Mn)、鎳(Ni)等的1種以上的金屬與銅的銅合金配線。作為如此的銅合金配線的具體例，可舉例如銅-鎂合金配線(CuMg合金配線)、銅-錳合金配線(CuMn合金配線)、銅-鎳合金配線(CuNi合金配線)等。 When the metal copper or the copper alloy of the present invention is a copper wiring or a copper alloy wiring, the term "copper alloy wiring" as used herein refers to a copper alloy wiring containing copper as a main component, and includes, for example, magnesium (Mg) and manganese (Mn). ) A copper alloy wiring of one or more metals such as nickel (Ni) and copper. Specific examples of the copper alloy wiring include copper-magnesium alloy wiring (CuMg alloy wiring), copper-manganese alloy wiring (CuMn alloy wiring), and copper-nickel alloy wiring (CuNi alloy wiring).
本發明的Ti系金屬為密合層時，本發明的半導體基板可具有Ti系金屬以外的阻隔金屬。作為該阻隔金屬的具體例，可舉例如鉭(Ta)、氮化鉭(TaN)等。 When the Ti-based metal of the present invention is an adhesion layer, the semiconductor substrate of the present invention may have a barrier metal other than the Ti-based metal. Specific examples of the barrier metal include tantalum (Ta), tantalum nitride (TaN), and the like.
本發明的半導體基板，可具有無鉛(Pb-free)焊料凸塊。此處，構成所謂無鉛焊料凸塊的金屬，可舉例如含選自銅(Cu)、錫(Sn)、鋁(Al)、鎳(Ni)、鋅(Zn)、銀(Ag)、金(Au)、銦(In)、銻(Sb)、鉍(Bi)等金屬者。無鉛(Pb-free)焊料凸塊為含金屬銅或銅合金的凸塊時，可舉例如含銅的凸塊或含選自錫(Sn)之1種以上的金屬與銅的銅合金凸塊。作為如此的銅合金凸塊的具體例，可舉例如銅-錫合金凸塊(CuSn合金凸塊)等。 The semiconductor substrate of the present invention may have a lead-free (Pb-free) solder bump. Here, the metal constituting the so-called lead-free solder bump may, for example, be selected from the group consisting of copper (Cu), tin (Sn), aluminum (Al), nickel (Ni), zinc (Zn), silver (Ag), and gold ( Metals such as Au), indium (In), antimony (Sb), and antimony (Bi). When the lead-free (Pb-free) solder bump is a bump containing a metal copper or a copper alloy, for example, a bump containing copper or a copper alloy bump containing one or more metals selected from tin (Sn) and copper may be used. . Specific examples of such copper alloy bumps include copper-tin alloy bumps (CuSn alloy bumps).
本發明的半導體基板，於具有含金屬銅或銅 合金的凸塊時，配線可為含金屬銅或銅合金以外的金屬的配線。作為構成該配線的金屬，可舉例如鋁(Al)、金(Au)等。作為如此配線的具體例，可舉例如鋁(Al)配線、金(Au)配線等。 The semiconductor substrate of the present invention has a metal-containing copper or copper In the case of bumps of the alloy, the wiring may be a wiring containing a metal other than metal copper or a copper alloy. Examples of the metal constituting the wiring include aluminum (Al), gold (Au), and the like. Specific examples of such wiring include aluminum (Al) wiring, gold (Au) wiring, and the like.
本發明的半導體基板，於具有無鉛(Pb-free)焊料凸塊時，該半導體基板為了提高上述金屬配線與該凸塊的接著性，該等之間可具有含鎳(Ni)、鈀(Pd)、銅(Cu)等金屬的導體/接著部位。 In the semiconductor substrate of the present invention, when a lead-free (Pb-free) solder bump is provided, the semiconductor substrate may have nickel (Ni) or palladium (Pd) in order to improve the adhesion between the metal wiring and the bump. ), a conductor/attachment of a metal such as copper (Cu).
作為形成上述阻隔金屬、密合層、金屬配線、無鉛(Pb-free)焊料凸塊、導體/接著部位之方法，只要是通常本領域所採行的方法即無特別限制，具體而言，例如於構成本發明的半導體基板的晶圓上，用光阻等形成電路後，採用鍍金、化學氣相蒸鍍，形成該阻隔金屬、密合層、金屬配線、無鉛(Pb-free)焊料凸塊、導體/接著部位。 The method for forming the barrier metal, the adhesion layer, the metal wiring, the lead-free (Pb-free) solder bump, and the conductor/adjoining portion is not particularly limited as long as it is generally employed in the art, specifically, for example, After forming a circuit with a photoresist or the like on a wafer constituting the semiconductor substrate of the present invention, the barrier metal, the adhesion layer, the metal wiring, and the lead-free (Pb-free) solder bump are formed by gold plating or chemical vapor deposition. , conductor / follow-up parts.
以下，基於實施例及比較例具體地說明本發明，惟本發明不限於該等範例。再者，以下例中之%，在無特別記載下，係重量基準(w/w)%。 Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to the examples. In addition, the % in the following examples are weight-based (w/w)% unless otherwise specified.
實施例1 本發明的蝕刻劑的調製-1 Example 1 Modification of the etchant of the present invention -1
於超純水中，添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表1所示的重量%，得到本 發明的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑1。 In ultrapure water, hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (manufactured by Italmatch Japan Co., Ltd.) ), potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (manufactured by Komatsuya Co., Ltd.), and appropriately stirred to obtain the weight % shown in Table 1, The etchant of the invention. The resulting etchant had a pH of 9.0. This etchant is the etchant 1.
比較例1 比較用的蝕刻劑的調製-1 Comparative Example 1 Modification of the etchant used for comparison-1
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、1-羥基乙烷-1,1-雙(膦酸)(60%水溶液)(和光純藥工業股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表1所示的重量%，得到比較用的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑2。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.), 1-hydroxyethane-1,1-bis(phosphonic acid) (60% aqueous solution) (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the ultrapure water. Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (manufactured by Komatsuya Co., Ltd.) were appropriately stirred to have a weight % shown in Table 1, and an etchant for comparison was obtained. The resulting etchant had a pH of 9.0. This etchant is the etchant 2.
比較例2 比較用的蝕刻劑的調製-2 Comparative Example 2 Modification of the etchant used for comparison-2
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、伸乙基二胺四乙酸(和光純藥工業股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表1所示的重量%，得到比較用的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑3。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries Co., Ltd.), ethyldiaminetetraacetic acid (manufactured by Wako Pure Chemical Industries Co., Ltd.), and potassium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd.) And citric acid (made by Komatsuya Co., Ltd.), and stirred suitably, and it made the weight-% shown by Table 1, and the etching agent for comparison was obtained. The resulting etchant had a pH of 9.0. This etchant is an etchant 3.
實施例1及比較例1至2的蝕刻劑的組成(成分及重量%)係示於表1。 The compositions (components and % by weight) of the etchants of Example 1 and Comparative Examples 1 to 2 are shown in Table 1.
實驗例1至3蝕刻劑1至3的浸漬實驗 Experimental examples 1 to 3 immersion experiments 1 to 3 impregnation experiments
將實施例1及比較例1至2所得之各蝕刻劑放入聚丙烯製容器，於加溫至40℃之該蝕刻劑中，將1cm×2cm的鈦板(Rare Metallic公司製)以及2cm×2cm的銅板(Rare Metallic公司製)各1片同時浸漬300分鐘。蝕刻中，每既定的時間(30、60、180、300分)，分別取樣100μL作為金屬含量分析用、100μL作為過氧化氫分析用。 Each of the etchants obtained in Example 1 and Comparative Examples 1 to 2 was placed in a polypropylene container, and a titanium plate (manufactured by Rare Metallic Co., Ltd.) of 1 cm × 2 cm and 2 cm × were placed in the etchant heated to 40 ° C. One piece of a 2 cm copper plate (manufactured by Rare Metallic Co., Ltd.) was simultaneously immersed for 300 minutes. In the etching, 100 μL of each of the predetermined time (30, 60, 180, and 300 minutes) was sampled for metal content analysis and 100 μL was used for hydrogen peroxide analysis.
取樣作為金屬含量分析用的各蝕刻劑，係用1%硝酸水溶液稀釋100倍，用電漿發光分光分析裝置(裝置名稱：ICP-AES SPS-3100；SII公司製)測定金屬鈦及金屬銅的含量。從測定的含量的結果，算出鈦板與銅板的每單位面積的金屬鈦及金屬銅的溶解量以及鈦及銅的蝕刻速度。其結 果表示於表2。 Each of the etchants for the analysis of the metal content was diluted 100 times with a 1% aqueous solution of nitric acid, and the titanium metal and the metal copper were measured by a plasma emission spectroscopic analyzer (device name: ICP-AES SPS-3100; manufactured by SII). content. From the results of the measured contents, the amount of dissolution of titanium metal and metallic copper per unit area of the titanium plate and the copper plate, and the etching rate of titanium and copper were calculated. Its knot The results are shown in Table 2.
而且，取樣作為過氧化氫分析用的各蝕刻劑，係用0.5N的硫酸水溶液定容為10mL，藉由0.02莫耳/升的過錳酸鉀之氧化還原滴定法算出過氧化氫的含量。其結果表示於表3。 Further, each of the etchants for hydrogen peroxide analysis was sampled to a volume of 10 mL with a 0.5 N aqueous sulfuric acid solution, and the content of hydrogen peroxide was calculated by a redox titration method of 0.02 mol/liter potassium permanganate. The results are shown in Table 3.
再者，該等實驗例，係分別將1片的鈦板及銅板持續浸漬最長300分鐘的實驗，惟本實驗例，係假設為於實際使用蝕刻劑時連續浸漬複數片的半導體基板的方法之示範實驗，為蝕刻複數片的半導體基板最長300分鐘，以比較連續使用相同的蝕刻劑的情況之蝕刻速度與過氧化氫的分解率者。 Furthermore, in these experimental examples, one piece of the titanium plate and the copper plate were continuously immersed for an experiment for up to 300 minutes, but this experimental example is assumed to be a method of continuously immersing a plurality of semiconductor substrates in the actual use of an etchant. The demonstration experiment is to etch a plurality of semiconductor substrates for a maximum of 300 minutes to compare the etching rate of the same etchant continuously with the decomposition rate of hydrogen peroxide.
由實驗例1至3的結果，得知本發明的蝕刻劑(蝕刻劑1)不只是Ti/Cu的溶解速度比高，從開始蝕刻到300分鐘後的過氧化氫的分解率，與其他蝕刻劑(蝕刻劑2及3)相比，最低為14.8%，而得知最能抑制過氧化氫的分解(實驗例1)。相對於此，得知比較例1的蝕刻劑(蝕刻劑2)，雖與本發明的蝕刻劑具有相同程度的Ti/Cu的溶解速度比，惟過氧化氫的分解率非常高，從開始蝕刻到300分鐘後，過氧化氫接近7成分解(實驗例2)。而且，得知比較例2的蝕刻劑(蝕刻劑3)之Ti/Cu的溶解速度比雖比本發明的蝕刻劑高，惟過氧化氫的分解率高，從開始蝕刻到300分鐘後，過氧化氫接近5成分解(實驗例3)。從實驗例1至3的銅蝕刻速度的結果來看，於任一情況下，從銅板有 溶出銅(氧化銅)者係以本發明的蝕刻劑所致之蝕刻之從銅板之銅(氧化銅)的溶出量最多。不過，因為本發明的蝕刻劑最能抑制過氧化氫的分解，所以認為本發明的螫合劑之構造中具有氮原子的膦酸系螫合劑對銅(氧化銅)具有最高的螫合能力，而藉由螫合銅(氧化銅)抑制(防止)過氧化氫的分解。 From the results of Experimental Examples 1 to 3, it was found that the etchant (etchant 1) of the present invention is not only a high dissolution rate ratio of Ti/Cu, but also a decomposition rate of hydrogen peroxide from the start of etching to 300 minutes, and other etching. The lowest ratio of the agent (etching agents 2 and 3) was 14.8%, and it was found that the decomposition of hydrogen peroxide was most suppressed (Experimental Example 1). On the other hand, the etchant (etching agent 2) of Comparative Example 1 was found to have a Ti/Cu dissolution rate ratio similar to that of the etchant of the present invention, but the decomposition rate of hydrogen peroxide was very high, and etching was started. After 300 minutes, hydrogen peroxide was decomposed by nearly 70% (Experimental Example 2). Further, it was found that the etching rate of Ti/Cu of the etchant (etching agent 3) of Comparative Example 2 was higher than that of the etchant of the present invention, but the decomposition rate of hydrogen peroxide was high, from the start of etching to 300 minutes. Hydrogen peroxide was nearly 50% decomposed (Experimental Example 3). From the results of the copper etching speeds of Experimental Examples 1 to 3, in either case, there is The copper (copper oxide) eluted by the etchant of the present invention has the largest amount of eluted copper (copper oxide) from the copper plate. However, since the etchant of the present invention most inhibits the decomposition of hydrogen peroxide, it is considered that the phosphonic acid-based chelating agent having a nitrogen atom in the structure of the chelating agent of the present invention has the highest affinity for copper (copper oxide), and The decomposition of hydrogen peroxide is suppressed (prevented) by copper (copper oxide).
實施例2 本發明的蝕刻劑的調製-2 Example 2 Modulation of an etchant of the present invention-2
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表4所示的重量%，得到本發明的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑4。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (manufactured by Komatsuya Co., Ltd.) were appropriately stirred to have a weight % shown in Table 4 to obtain an etchant of the present invention. The resulting etchant had a pH of 9.0. This etchant is an etchant 4.
比較例3 比較用的蝕刻劑的調製-3 Comparative Example 3 Modification of the etchant used for comparison-3
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及酒石酸(和光純藥工業股份有限公司製)，並適當地攪拌，使其成為表4所示的重量%，得到比較用的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑5。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and tartaric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were appropriately stirred to have a weight % shown in Table 4, and an etchant for comparison was obtained. The resulting etchant had a pH of 9.0. This etchant is an etchant 5.
比較例4 比較用的蝕刻劑的調製-4 Comparative Example 4 Modification of the etchant used for comparison-4
於超純水中添加過氧化氫(和光純藥工業股份有限公 司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及蘋果酸(和光純藥工業股份有限公司製)，並適當地攪拌，使其成為表4所示的重量%，得到比較用的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑6。 Adding hydrogen peroxide to ultrapure water (Waguang Pure Pharmaceutical Industry Co., Ltd. )), di-ethyltriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (Italmatch Japan Co., Ltd.), potassium hydroxide (made by Wako Pure Chemical Industries Co., Ltd.) and apple The acid (manufactured by Wako Pure Chemical Industries, Ltd.) was appropriately stirred to have a weight % shown in Table 4, and an etchant for comparison was obtained. The resulting etchant had a pH of 9.0. This etchant is an etchant 6.
比較例5 比較用的蝕刻劑的調製-5 Comparative Example 5 Modification of the etchant used for comparison-5
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及1,2,3-丙三甲酸(和光純藥工業股份有限公司製)，並適當地攪拌，使其成為表4所示的重量%，得到比較用的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑7。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and 1,2,3-propane tricarboxylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and appropriately stirred to make it a weight % shown in Table 4. , an etchant for comparison is obtained. The resulting etchant had a pH of 9.0. This etchant is an etchant 7.
比較例6 比較用的蝕刻劑的調製-6 Comparative Example 6 Modification of the etchant used for comparison-6
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及苯并***(和光純藥工業股份有限公司製)，並適當地攪拌，使其成為表4所示的重量%，得到比較用的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑8。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and benzotriazole (manufactured by Wako Pure Chemical Industries, Ltd.), and appropriately stirred to obtain the weight % shown in Table 4, and used for comparison. Etchant. The resulting etchant had a pH of 9.0. This etchant is an etchant 8.
實施例2及比較例3至6的蝕刻劑的組成(成分及重量%)，表示於表4。 The compositions (components and % by weight) of the etchants of Example 2 and Comparative Examples 3 to 6 are shown in Table 4.
實驗例4至8蝕刻劑4至8的浸漬實驗 Experimental examples 4 to 8 immersion experiments 4 to 8 impregnation experiments
將實施例2及比較例3至6所得之各蝕刻劑放入聚丙烯製容器，於該蝕刻劑中，於室溫(25℃)下，將2cm×2cm的鈦板(Rare Metallic公司製)以及2cm×2cm的銅板(Rare Metallic公司製)各2片同時浸漬300分鐘。蝕刻中，每既定的時間(60、120、180、240、300分)，分別取樣100μL作為金屬含量分析用、100μL作為過氧化氫分析用。 Each of the etchants obtained in Example 2 and Comparative Examples 3 to 6 was placed in a polypropylene container, and a 2 cm × 2 cm titanium plate (manufactured by Rare Metallic Co., Ltd.) was placed in the etchant at room temperature (25 ° C). Two sheets of 2 cm × 2 cm copper plates (manufactured by Rare Metallic Co., Ltd.) were simultaneously immersed for 300 minutes. During the etching, 100 μL of each of the predetermined time (60, 120, 180, 240, and 300 minutes) was sampled for metal content analysis and 100 μL was used for hydrogen peroxide analysis.
取樣作為金屬含量分析用的各蝕刻劑，係用1%硝酸水溶液稀釋100倍，用電漿發光分光分析裝置(裝置名稱：ICP-AES SPS-3100；SII公司製)測定金屬鈦及金屬銅的含量。從測定的含量的結果，算出鈦板與銅板的每單位面積的金屬鈦及金屬銅的溶解量以及鈦及銅的蝕刻速度。其結果表示於表5。 Each of the etchants for the analysis of the metal content was diluted 100 times with a 1% aqueous solution of nitric acid, and the titanium metal and the metal copper were measured by a plasma emission spectroscopic analyzer (device name: ICP-AES SPS-3100; manufactured by SII). content. From the results of the measured contents, the amount of dissolution of titanium metal and metallic copper per unit area of the titanium plate and the copper plate, and the etching rate of titanium and copper were calculated. The results are shown in Table 5.
而且，取樣作為過氧化氫分析用的各蝕刻劑，用0.5N的硫酸水溶液定容為10mL，藉由0.02莫耳/升的過錳酸鉀之氧化還原滴定法算出過氧化氫的含量。其結果表示於表6。 Further, each of the etchants for hydrogen peroxide analysis was sampled, and the volume was adjusted to 10 mL with a 0.5 N aqueous sulfuric acid solution, and the content of hydrogen peroxide was calculated by a redox titration method of 0.02 mol/liter potassium permanganate. The results are shown in Table 6.
再者，該等實驗例，係分別將2片的鈦板及銅板持續浸漬最長300分鐘的實驗，惟本實驗例，係假設為於實際使用蝕刻劑時連續浸漬複數片的半導體基板的方法之示範實驗，為蝕刻複數片的半導體基板最長300分鐘，以比較連續使用相同的蝕刻劑的情況之蝕刻速度與過氧化氫的分解率者。 Furthermore, in these experimental examples, two titanium plates and copper plates were continuously impregnated for a maximum of 300 minutes, but this experimental example is assumed to be a method of continuously impregnating a plurality of semiconductor substrates when an etchant is actually used. The demonstration experiment is to etch a plurality of semiconductor substrates for a maximum of 300 minutes to compare the etching rate of the same etchant continuously with the decomposition rate of hydrogen peroxide.
由實驗例4至8的結果得知，本發明的蝕刻 劑(蝕刻劑4)，從開始蝕刻到300分鐘後的過氧化氫的分解率與其他蝕刻劑(蝕刻劑5至8)相比，最低為7.8%，得知最能抑制過氧化氫的分解(實驗例4)。由實驗例4至7的銅蝕刻速度的結果，得知於連續長時間使用蝕刻劑的情況，本發明的蝕刻劑所致之蝕刻，最能抑制從銅板之銅(氧化銅)的溶出量。由該等，認為有機酸(銅抗蝕劑)中，本發明的有機酸(銅抗蝕劑)之具有至少1個羥基及至少3個羧基的有機酸(銅抗蝕劑)最能抑制源自銅之銅(氧化銅)的溶出，進而可抑制銅(氧化銅)所致之過氧化氫的分解。而且，得知與含有傳統習知的銅抗蝕劑之苯并***之蝕刻劑(蝕刻劑8)相比，於連續長時間使用蝕刻劑時，本發明的蝕刻劑會抑制過氧化氫的分解。 From the results of Experimental Examples 4 to 8, it is known that the etching of the present invention The agent (etchant 4) has a decomposition rate of hydrogen peroxide of 300% from the start of etching to 300 minutes, and the lowest rate is 7.8%. It is known that the decomposition of hydrogen peroxide is most suppressed. (Experimental Example 4). As a result of the copper etching rates of Experimental Examples 4 to 7, it was found that the etching by the etchant of the present invention can most effectively suppress the elution amount of copper (copper oxide) from the copper plate in the case where the etchant is used continuously for a long period of time. Among these, it is considered that among organic acids (copper resists), the organic acid (copper resist) of the organic acid (copper resist) of the present invention having at least one hydroxyl group and at least three carboxyl groups (copper resist) is the most effective source of suppression. The elution of copper (copper oxide) from copper further suppresses the decomposition of hydrogen peroxide by copper (copper oxide). Further, it is known that the etchant of the present invention suppresses hydrogen peroxide when the etchant is used continuously for a long period of time as compared with an etchant (etchant 8) containing a conventional conventional copper resist benzotriazole. break down.
比較例7 比較用的蝕刻劑的調製-7 Comparative Example 7 Modulation of the etchant used for comparison-7
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及苯并***(和光純藥工業股份有限公司製)，並適當地攪拌，使其成為表7所示的重量%，得到比較用的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑9。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and benzotriazole (manufactured by Wako Pure Chemical Industries, Ltd.), and appropriately stirred to obtain the weight % shown in Table 7, and used for comparison. Etchant. The resulting etchant had a pH of 9.0. This etchant is an etchant 9.
比較例8 比較用的蝕刻劑的調製-8 Comparative Example 8 Modification of the etchant used for comparison -8
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、伸乙基二胺(和光純藥工業股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋 股份有限公司製)，使其成為表7所示的重量%後，因過氧化氫與伸乙基二胺激烈地反應，導致過氧化氫急速分解，而無法得到比較用的蝕刻劑10。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries Co., Ltd.), ethylidene diamine (manufactured by Wako Pure Chemical Industries Co., Ltd.), potassium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd.), and Citric acid After the weight % shown in Table 7 was obtained, the hydrogen peroxide reacted violently with the ethylene diamine to cause rapid decomposition of hydrogen peroxide, and the etching agent 10 for comparison could not be obtained.
比較例9 比較用的蝕刻劑的調製-9 Comparative Example 9 Modulation of the etchant used for comparison -9
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、乙醇胺(和光純藥工業股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，使其成為表7所示的重量%後，因過氧化氫與乙醇胺激烈地反應，導致過氧化氫急速分解，而無法得到比較用的蝕刻劑11。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries Co., Ltd.), ethanolamine (manufactured by Wako Pure Chemical Industries Co., Ltd.), potassium hydroxide (manufactured by Wako Pure Chemical Industries Co., Ltd.), and citric acid (small) were added to ultrapure water. After being made up to the weight % shown in Table 7, the Matsuzawa Co., Ltd. reacted violently with hydrogen peroxide and ethanolamine, and the hydrogen peroxide was rapidly decomposed, and the etchant 11 for comparison was not obtained.
合併表示比較例7至9的蝕刻劑的組成(成分及重量%)與實施例1的蝕刻劑的組成於表7。 The composition (component and wt%) of the etchant of Comparative Examples 7 to 9 and the composition of the etchant of Example 1 were combined in Table 7.
實驗例9 蝕刻劑9的浸漬實驗 Experimental Example 9 Impregnation experiment of etchant 9
將比較例7所得之蝕刻劑放入聚丙烯製容器，於加溫至40℃之該蝕刻劑中，將1cm×2cm的鈦板(Rare Metallic公司製)以及2cm×2cm的銅板(Rare Metallic公司製)各1片同時浸漬300分鐘。蝕刻中，每既定的時間(30、60、180、300分)，分別取樣100μL作為金屬含量分析用、100μL作為過氧化氫分析用。 The etchant obtained in Comparative Example 7 was placed in a polypropylene container, and a 1 cm × 2 cm titanium plate (manufactured by Rare Metallic Co., Ltd.) and a 2 cm × 2 cm copper plate (Rare Metallic Co., Ltd.) were added to the etchant heated to 40 °C. Each of the sheets was simultaneously immersed for 300 minutes. In the etching, 100 μL of each of the predetermined time (30, 60, 180, and 300 minutes) was sampled for metal content analysis and 100 μL was used for hydrogen peroxide analysis.
取樣作為金屬含量分析用的各蝕刻劑，係用1%硝酸水溶液稀釋100倍，用電漿發光分光分析裝置(裝置名稱：ICP-AES SPS-3100；SII公司製)測定金屬鈦及金屬銅的含量。從測定的含量的結果，算出鈦板與銅板的每單位面積的金屬鈦及金屬銅的溶解量以及鈦及銅的蝕刻速度。其結果與實驗例1的結果合併表示於表8。 Each of the etchants for the analysis of the metal content was diluted 100 times with a 1% aqueous solution of nitric acid, and the titanium metal and the metal copper were measured by a plasma emission spectroscopic analyzer (device name: ICP-AES SPS-3100; manufactured by SII). content. From the results of the measured contents, the amount of dissolution of titanium metal and metallic copper per unit area of the titanium plate and the copper plate, and the etching rate of titanium and copper were calculated. The results are shown in Table 8 in combination with the results of Experimental Example 1.
而且，取樣作為過氧化氫分析用的蝕刻劑，係用0.5N的硫酸水溶液定容為10mL，藉由0.02莫耳/升的過錳酸鉀之氧化還原滴定法算出過氧化氫的含量。其結果與實驗例1的結果合併表示於表9。 Further, sampling was carried out as an etchant for hydrogen peroxide analysis, and the volume was adjusted to 10 mL with a 0.5 N aqueous sulfuric acid solution, and the content of hydrogen peroxide was calculated by a redox titration method of 0.02 mol/liter potassium permanganate. The results are shown in Table 9 in combination with the results of Experimental Example 1.
再者，本實驗例係分別將1片的鈦板及銅板持續浸漬最長300分鐘的實驗，惟本實驗例，係假設為於實際使用蝕刻劑時連續浸漬複數片的半導體基板的方法之示範實驗，為蝕刻複數片的半導體基板最長300分鐘，以比較連續使用相同的蝕刻劑的情況之蝕刻速度與過氧化氫的分解率者。 Furthermore, in this experimental example, one piece of titanium plate and copper plate were continuously impregnated for a maximum of 300 minutes, but this experimental example is assumed to be a demonstration experiment of a method of continuously impregnating a plurality of semiconductor substrates while actually using an etchant. In order to etch a plurality of semiconductor substrates for a maximum of 300 minutes, the etching rate and the decomposition rate of hydrogen peroxide in the case of continuously using the same etchant are compared.
實驗例9的蝕刻劑(蝕刻劑9)，本發明的螫合 劑之二伸乙基三胺五(亞甲基膦酸)的含量與實驗例8的蝕刻劑(蝕刻劑8)相比，係少0.3重量%，為1.5重量%，確認到從銅板的銅(氧化銅)的溶出量對過氧化氫的分解帶來何種程度的影響。由實驗例1及9的結果得知，與含有傳統習知的銅抗蝕劑之苯并***之蝕刻劑(蝕刻劑9)相比，本發明的蝕刻劑(蝕刻劑1)所致之蝕刻，從銅板之銅(氧化銅)的總溶出量變多。實驗例1的本發明的蝕刻劑(蝕刻劑1)與實驗例9的蝕刻劑(蝕刻劑9)，由於只有銅抗蝕劑不同，故單就銅抗蝕劑的抗蝕效果的觀點而言，實驗例9的蝕刻劑(蝕刻劑9)所致之蝕刻，因從銅板之銅(氧化銅)的溶出量少，應可抑制過氧化氫的分解。但是，由表9的結果得知，相反地，與實驗例1的本發明的蝕刻劑(蝕刻劑1)相比，實驗例9的蝕刻劑(蝕刻劑9)係得到過氧化氫的分解大約以2倍速度進行的結果。詳細狀況雖不確定，惟提示苯并***對過氧化氫有不良的影響，並不表示若是抑制源自金屬銅或銅合金之銅(氧化銅)的溶出，即可抑制過氧化氫的分解。而且，由比較例8及9的結果得知，含有傳統習知的螫合劑之伸乙基二胺之蝕刻劑(蝕刻劑10)以及含有乙醇胺之蝕刻劑(蝕刻劑11)中，該等螫合劑會與過氧化氫反應，導致得到過氧化氫急速分解的結果。由該等結果，可知：銅抗蝕劑並非只要是可抑制源自金屬銅或銅合金之銅(氧化銅)的溶出者皆可，而需為對過氧化氫不帶來不良影響，可有效地抑制源自金屬銅或銅合金之銅(氧化銅)的溶出者，而且，螫合劑並非只要是可補充(螫合)銅(氧化銅)者皆可，而 需為對過氧化氫不帶來不良影響、可有效地補充(螫合)銅(氧化銅)者。由於以上原因，為了抑制過氧化氫的分解且選擇性地蝕刻Ti系金屬，需選擇檸檬酸等本發明的有機酸作為銅抗蝕劑，需選擇構造中具有氮原子的膦酸系螫合劑作為螫合劑。 Etching agent (etching agent 9) of Experimental Example 9, the combination of the present invention The content of the diethyltriamine penta (methylene phosphonic acid) of the agent was 0.3% by weight less than that of the etchant (etching agent 8) of Experimental Example 8, and was 1.5% by weight, and copper from the copper plate was confirmed. The extent to which the amount of (copper oxide) is dissolved affects the decomposition of hydrogen peroxide. From the results of Experimental Examples 1 and 9, it was found that the etchant (etchant 1) of the present invention was caused by an etchant (etchant 9) containing a conventional conventional copper resist benzotriazole. Etching, the total amount of copper (copper oxide) from the copper plate is increased. The etchant (etchant 1) of the present invention in Experimental Example 1 and the etchant (etchant 9) of Experimental Example 9 differ only in terms of the corrosion resistance of the copper resist because only the copper resist is different. In the etching by the etchant (etching agent 9) of Experimental Example 9, the amount of elution of copper (copper oxide) from the copper plate was small, and decomposition of hydrogen peroxide should be suppressed. However, as is apparent from the results of Table 9, on the contrary, the etchant (etching agent 9) of Experimental Example 9 was decomposed by hydrogen peroxide in comparison with the etchant (etching agent 1) of the present invention of Experimental Example 1. Results at 2x speed. Although the detailed situation is uncertain, it suggests that benzotriazole has a bad influence on hydrogen peroxide. It does not mean that the inhibition of hydrogen peroxide decomposition can be inhibited by inhibiting the dissolution of copper (copper oxide) derived from metallic copper or copper alloy. . Further, from the results of Comparative Examples 8 and 9, it was found that the etchant (etching agent 10) containing the conventionally known chelating agent, and the etchant (etching agent 11) containing ethanolamine, The mixture will react with hydrogen peroxide, resulting in a rapid decomposition of hydrogen peroxide. From these results, it is understood that the copper resist is not limited as long as it can suppress copper (copper oxide) derived from metallic copper or a copper alloy, and it is effective for not adversely affecting hydrogen peroxide. To suppress the dissolution of copper (copper oxide) derived from metallic copper or copper alloy, and the chelating agent is not limited to copper (copper oxide). Those who do not adversely affect hydrogen peroxide and can effectively replenish (combined) copper (copper oxide). For the above reasons, in order to suppress the decomposition of hydrogen peroxide and selectively etch the Ti-based metal, it is necessary to select an organic acid of the present invention such as citric acid as a copper resist, and it is necessary to select a phosphonic acid-based chelating agent having a nitrogen atom in the structure. Mixing agent.
實施例3至6本發明的蝕刻劑的調製-3至6 Examples 3 to 6 Modification of the etchant of the present invention - 3 to 6
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表10所示的重量%，分別得到本發明的蝕刻劑。所得之蝕刻劑的pH為9.0。該等蝕刻劑為蝕刻劑12至15。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (manufactured by Komatsuya Co., Ltd.) were appropriately stirred to obtain weight % shown in Table 10, and the etchant of the present invention was obtained. The resulting etchant had a pH of 9.0. These etchants are etchants 12 to 15.
實施例3至6的蝕刻劑的組成(成分及重量%)係示於表10。 The compositions (components and % by weight) of the etchants of Examples 3 to 6 are shown in Table 10.
實驗例10至13蝕刻劑12至15的浸漬實驗 Experimental examples 10 to 13 immersion experiments 12 to 15 impregnation experiments
將實施例3至6所得之各蝕刻劑放入聚丙烯製容器，於加溫至40℃之該蝕刻劑中，將1cm×2cm的鈦板(Rare Metallic公司製)以及2cm×2cm的銅板(Rare Metallic公司製)各1片同時浸漬300分鐘。蝕刻中，每既定的時間(30、60、180、300分)，分別取樣100μL作為金屬含量分析用、100μL作為過氧化氫分析用。 Each of the etchants obtained in Examples 3 to 6 was placed in a polypropylene container, and a titanium plate (manufactured by Rare Metallic Co., Ltd.) and a 2 cm × 2 cm copper plate of 1 cm × 2 cm were placed in the etchant heated to 40 ° C ( Each piece of Rare Metallic Co., Ltd. was immersed for 300 minutes at the same time. In the etching, 100 μL of each of the predetermined time (30, 60, 180, and 300 minutes) was sampled for metal content analysis and 100 μL was used for hydrogen peroxide analysis.
取樣作為金屬含量分析用的各蝕刻劑，係用1%硝酸水溶液稀釋100倍，用電漿發光分光分析裝置(裝置名稱：ICP-AES SPS-3100；SII公司製)測定金屬鈦及金屬銅的含量。從測定的含量的結果，算出鈦板與銅板的每單位面積的金屬鈦及金屬銅的溶解量以及鈦及銅的蝕刻速度。其結果表示於表11。 Each of the etchants for the analysis of the metal content was diluted 100 times with a 1% aqueous solution of nitric acid, and the titanium metal and the metal copper were measured by a plasma emission spectroscopic analyzer (device name: ICP-AES SPS-3100; manufactured by SII). content. From the results of the measured contents, the amount of dissolution of titanium metal and metallic copper per unit area of the titanium plate and the copper plate, and the etching rate of titanium and copper were calculated. The results are shown in Table 11.
而且，取樣作為過氧化氫分析用的各蝕刻劑，係用0.5N的硫酸水溶液定容為10mL，藉由0.02莫耳/升的過錳酸鉀之氧化還原滴定法算出過氧化氫的含量。其結果表示於表12。 Further, each of the etchants for hydrogen peroxide analysis was sampled to a volume of 10 mL with a 0.5 N aqueous sulfuric acid solution, and the content of hydrogen peroxide was calculated by a redox titration method of 0.02 mol/liter potassium permanganate. The results are shown in Table 12.
再者，該等實驗例係分別將1片的鈦板及銅板，持續浸漬最長300分鐘的實驗，惟本實驗例，係假設為於實際使用蝕刻劑時連續浸漬複數片的半導體基板的方法之示範實驗，為蝕刻複數片的半導體基板最長300分鐘，以比較連續使用相同的蝕刻劑的情況之蝕刻速度與過氧化氫的分解率者。 Furthermore, in the experimental examples, one piece of the titanium plate and the copper plate were continuously impregnated for a maximum of 300 minutes, but this experimental example is assumed to be a method of continuously immersing a plurality of semiconductor substrates in the actual use of an etchant. The demonstration experiment is to etch a plurality of semiconductor substrates for a maximum of 300 minutes to compare the etching rate of the same etchant continuously with the decomposition rate of hydrogen peroxide.
由實驗例10至13的結果得知，本發明的螫合劑之含量越多，越可抑制銅(氧化銅)所致之過氧化氫的分解。而且，使用任一蝕刻劑的蝕刻，皆具有高Ti/Cu的溶解速度比，且可抑制過氧化氫的分解。 From the results of Experimental Examples 10 to 13, it was found that the more the content of the chelating agent of the present invention, the more the decomposition of hydrogen peroxide by copper (copper oxide) can be suppressed. Moreover, etching using any etchant has a high Ti/Cu dissolution rate ratio and can suppress decomposition of hydrogen peroxide.
實施例7 本發明的蝕刻劑的調製-7 Example 7 Modulation of the etchant of the present invention-7
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鈉(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)， 並適當地攪拌，使其成為表13所示的重量%，得到本發明的蝕刻劑。所得之蝕刻劑的pH為9.2。該蝕刻劑為蝕刻劑16。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. , sodium hydroxide (made by Wako Pure Chemical Industries Co., Ltd.) and citric acid (made by Komatsuya Co., Ltd.), The mixture was appropriately stirred to have a weight % shown in Table 13, and an etchant of the present invention was obtained. The resulting etchant had a pH of 9.2. The etchant is an etchant 16.
實施例8 本發明的蝕刻劑的調製-8 Example 8 Modulation of an etchant of the present invention - 8
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鈉(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表13所示的重量%，得到本發明的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑17。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. Sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (manufactured by Komatsuya Co., Ltd.) were appropriately stirred to have a weight % shown in Table 13, and an etchant of the present invention was obtained. The resulting etchant had a pH of 9.0. This etchant is an etchant 17.
實施例9 本發明的蝕刻劑的調製-9 Example 9 Modulation of the etchant of the present invention-9
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鋰(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表13所示的重量%，得到本發明的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑18。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. Lithium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (manufactured by Komatsuya Co., Ltd.) were appropriately stirred to have a weight % shown in Table 13, and an etchant of the present invention was obtained. The resulting etchant had a pH of 9.0. This etchant is an etchant 18.
實施例7至9的蝕刻劑的組成(成分及重量%)與實施例1的蝕刻劑的組成係合併表示於表13。 The composition (component and wt%) of the etchant of Examples 7 to 9 and the composition of the etchant of Example 1 are shown in Table 13.
實驗例14至16蝕刻劑16至18的浸漬實驗 Experimental examples 14 to 16 immersion experiments 16 to 18 impregnation experiments
將實施例7至9所得之各蝕刻劑放入聚丙烯製容器，於加溫至40℃之該蝕刻劑中，將1cm×2cm的鈦板(Rare Metallic公司製)以及2cm×2cm的銅板(Rare Metallic公司製)各1片同時浸漬300分鐘。蝕刻中，每既定的時間(30、60、180、300分)，分別取樣100μL作為金屬含量分析用、100μL作為過氧化氫分析用。 Each of the etchants obtained in Examples 7 to 9 was placed in a polypropylene container, and a titanium plate (manufactured by Rare Metallic Co., Ltd.) and a 2 cm × 2 cm copper plate of 1 cm × 2 cm were placed in the etchant heated to 40 ° C ( Each piece of Rare Metallic Co., Ltd. was immersed for 300 minutes at the same time. In the etching, 100 μL of each of the predetermined time (30, 60, 180, and 300 minutes) was sampled for metal content analysis and 100 μL was used for hydrogen peroxide analysis.
取樣作為金屬含量分析用的各蝕刻劑，係用1%硝酸水溶液稀釋100倍，用電漿發光分光分析裝置(裝置名稱：ICP-AES SPS-3100；SII公司製)測定金屬鈦及金屬銅的含 量。從測定的含量的結果，算出鈦板與銅板的每單位面積的金屬鈦及金屬銅的溶解量以及鈦及銅的蝕刻速度。其結果表示於表14。 Each of the etchants for the analysis of the metal content was diluted 100 times with a 1% aqueous solution of nitric acid, and the titanium metal and the metal copper were measured by a plasma emission spectroscopic analyzer (device name: ICP-AES SPS-3100; manufactured by SII). Contain the amount. From the results of the measured contents, the amount of dissolution of titanium metal and metallic copper per unit area of the titanium plate and the copper plate, and the etching rate of titanium and copper were calculated. The results are shown in Table 14.
而且，取樣作為過氧化氫分析用的各蝕刻劑，係用0.5N的硫酸水溶液定容為10mL，藉由0.02莫耳/升的過錳酸鉀之氧化還原滴定法算出過氧化氫的含量。其結果表示於表15。 Further, each of the etchants for hydrogen peroxide analysis was sampled to a volume of 10 mL with a 0.5 N aqueous sulfuric acid solution, and the content of hydrogen peroxide was calculated by a redox titration method of 0.02 mol/liter potassium permanganate. The results are shown in Table 15.
再者，該等實驗例係分別將1片的鈦板及銅板，持續浸漬最長300分鐘的實驗，惟本實驗例，係假設為於實際使用蝕刻劑時連續浸漬複數片的半導體基板的方法之示範實驗，為蝕刻複數片的半導體基板最長300分鐘，以比較連續使用相同的蝕刻劑的情況之蝕刻速度與過氧化氫的分解率者。 Furthermore, in the experimental examples, one piece of the titanium plate and the copper plate were continuously impregnated for a maximum of 300 minutes, but this experimental example is assumed to be a method of continuously immersing a plurality of semiconductor substrates in the actual use of an etchant. The demonstration experiment is to etch a plurality of semiconductor substrates for a maximum of 300 minutes to compare the etching rate of the same etchant continuously with the decomposition rate of hydrogen peroxide.
由實驗例1以及14至16的結果得知，本發明的鹼金屬氫氧化物中，含有氫氧化鋰及氫氧化鈉的蝕刻劑(蝕刻劑16至18)之蝕刻，鈦的蝕刻速度高，結果係具有高Ti/Cu的溶解速度比。而且，得知該蝕刻劑與含有氫氧化鉀的蝕刻劑(蝕刻劑1)相比，可將過氧化氫的分解抑制在相同程度以下。由該等結果，得知本發明的鹼金屬氫氧化物中，氫氧化鋰及氫氧化鈉為較理想的鹼金屬氫氧化物。 From the results of Experimental Examples 1 and 14 to 16, it was found that the alkali metal hydroxide of the present invention is etched with an etchant (etching agent 16 to 18) containing lithium hydroxide and sodium hydroxide, and the etching rate of titanium is high. The result is a high Ti/Cu dissolution rate ratio. Further, it was found that the etchant can suppress the decomposition of hydrogen peroxide to the same level or less as compared with the etchant containing potassium hydroxide (etching agent 1). From these results, it was found that lithium hydroxide and sodium hydroxide are preferred alkali metal hydroxides in the alkali metal hydroxide of the present invention.
實施例10 本發明的蝕刻劑的調製-10 Example 10 Modulation of the etchant of the present invention -10
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、二伸乙基三胺五(亞甲基膦酸)7鈉鹽(32%水溶液)(Italmatch Japan股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表16所示的重量%，得到本發明的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑19。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and diamethylenetriamine penta (methylene phosphonic acid) 7 sodium salt (32% aqueous solution) (made by Italmatch Japan Co., Ltd.) were added to the ultrapure water. Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (manufactured by Komatsuya Co., Ltd.) were appropriately stirred to have a weight % shown in Table 16, and an etchant of the present invention was obtained. The resulting etchant had a pH of 9.0. This etchant is an etchant 19.
實施例11 本發明的蝕刻劑的調製-11 Example 11 Modulation of an etchant of the present invention-11
於超純水中添加過氧化氫(和光純藥工業股份有限公 司製)、伸乙基二胺四(亞甲基膦酸)(同人化學研究所股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表16所示的重量%，得到本發明的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑20。 Adding hydrogen peroxide to ultrapure water (Waguang Pure Pharmaceutical Industry Co., Ltd. )), Ethyldiaminetetrakis (methylenephosphonic acid) (manufactured by Homo Scientific Research Co., Ltd.), Potassium Hydroxide (made by Wako Pure Chemical Industries Co., Ltd.), and Citric Acid (Komatsuya Co., Ltd.) The solution was appropriately stirred to have a weight % shown in Table 16 to obtain an etchant of the present invention. The resulting etchant had a pH of 9.0. This etchant is an etchant 20.
實施例12 本發明的蝕刻劑的調製-12 Example 12 Modulation of an etchant of the present invention-12
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、硝基參(亞甲基膦酸)(50%水溶液)(東京化成工業股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表16所示的重量%，得到本發明的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑21。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries Co., Ltd.), nitroxylene (methylene phosphonic acid) (50% aqueous solution) (manufactured by Tokyo Chemical Industry Co., Ltd.), and potassium hydroxide (and potassium hydroxide) were added to ultrapure water. Was prepared by Wako Pure Chemical Industries, Ltd. and citric acid (manufactured by Komatsuya Co., Ltd.) and appropriately stirred to have a weight % shown in Table 16, and an etchant of the present invention was obtained. The resulting etchant had a pH of 9.0. This etchant is an etchant 21.
比較例10 比較用的蝕刻劑的調製-10 Comparative Example 10 Modification of the etchant used for comparison -10
於超純水中添加過氧化氫(和光純藥工業股份有限公司製)、1-羥基乙烷-1,1-雙(膦酸)(60%水溶液)(和光純藥工業股份有限公司製)、氫氧化鉀(和光純藥工業股份有限公司製)以及檸檬酸(小松屋股份有限公司製)，並適當地攪拌，使其成為表16所示的重量%，得到本發明的蝕刻劑。所得之蝕刻劑的pH為9.0。該蝕刻劑為蝕刻劑22。 Hydrogen peroxide (manufactured by Wako Pure Chemical Industries, Ltd.), 1-hydroxyethane-1,1-bis(phosphonic acid) (60% aqueous solution) (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the ultrapure water. Potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid (manufactured by Komatsuya Co., Ltd.) were appropriately stirred to have a weight % shown in Table 16, and an etchant of the present invention was obtained. The resulting etchant had a pH of 9.0. The etchant is an etchant 22.
實施例10至12以及比較例10的蝕刻劑的組成(成分及重量%)表示於表16。 The compositions (components and % by weight) of the etchants of Examples 10 to 12 and Comparative Example 10 are shown in Table 16.
實驗例17至20蝕刻劑19至22的浸漬實驗 Experimental Examples 17 to 20 Impregnation experiments of etchants 19 to 22
將實施例10至12以及比較例10所得之各蝕刻劑放入聚丙烯製容器，於加溫至40℃之該蝕刻劑中，將3cm×2cm的鈦板(Rare Metallic公司製)以及4cm×2cm的銅板(Rare Metallic公司製)各1片同時浸漬300分鐘。蝕刻中，每既定的時間(30、60、180、300分)，分別取樣100μL作為金屬含量分析用、100μL作為過氧化氫分析用。 Each of the etchants obtained in Examples 10 to 12 and Comparative Example 10 was placed in a polypropylene container, and a titanium plate (manufactured by Rare Metallic Co., Ltd.) of 3 cm × 2 cm and 4 cm × were placed in the etchant heated to 40 ° C. One piece of a 2 cm copper plate (manufactured by Rare Metallic Co., Ltd.) was simultaneously immersed for 300 minutes. In the etching, 100 μL of each of the predetermined time (30, 60, 180, and 300 minutes) was sampled for metal content analysis and 100 μL was used for hydrogen peroxide analysis.
取樣作為金屬含量分析用的各蝕刻劑，係用1%硝酸水溶液稀釋100倍，用電漿發光分光分析裝置(裝置名稱：ICP-AES SPS-3100；SII公司製)測定金屬鈦及金屬銅的含量。從測定的含量的結果，算出鈦板與銅板的每單位面積 的金屬鈦及金屬銅的溶解量以及鈦及銅的蝕刻速度。其結果表示於表17。 Each of the etchants for the analysis of the metal content was diluted 100 times with a 1% aqueous solution of nitric acid, and the titanium metal and the metal copper were measured by a plasma emission spectroscopic analyzer (device name: ICP-AES SPS-3100; manufactured by SII). content. Calculate the area per unit area of the titanium plate and the copper plate from the measured content The amount of metal titanium and copper metal dissolved and the etching rate of titanium and copper. The results are shown in Table 17.
而且，取樣作為過氧化氫分析用的各蝕刻劑，係用0.5N的硫酸水溶液定容為10mL，藉由0.02莫耳/升的過錳酸鉀之氧化還原滴定法算出過氧化氫的含量。其結果表示於表18。 Further, each of the etchants for hydrogen peroxide analysis was sampled to a volume of 10 mL with a 0.5 N aqueous sulfuric acid solution, and the content of hydrogen peroxide was calculated by a redox titration method of 0.02 mol/liter potassium permanganate. The results are shown in Table 18.
再者，該等實驗例係分別將1片的鈦板及銅板，持續浸漬最長300分鐘的實驗，係以與實驗例1至16的實驗條件相比，鈦板的面積為1.5倍至3倍以及銅板的面積為2倍實施之例。本實驗例，係以比實際使用蝕刻劑時嚴苛的條件之示範實驗，為確認因螫合劑的不同所致之過氧化氫的分解抑制效果不同者。 Furthermore, in the experimental examples, one piece of the titanium plate and the copper plate were continuously impregnated for a maximum of 300 minutes, and the area of the titanium plate was 1.5 to 3 times as compared with the experimental conditions of the experimental examples 1 to 16. And the case where the area of the copper plate is doubled. In this experimental example, it was confirmed that the decomposition inhibitory effect of hydrogen peroxide due to the difference in the chelating agent was different in an exemplary experiment under the harsh conditions when the etchant was actually used.
由實驗例17至19的結果得知，本發明的螫合劑中，就過氧化氫的分解抑制效果之點而言，係以含有二伸乙基三胺五(亞甲基膦酸)之蝕刻劑(蝕刻劑19)以及含有硝基參(亞甲基膦酸)之蝕刻劑(蝕刻劑21)較理想，以含有硝基參(亞甲基膦酸)之蝕刻劑(蝕刻劑21)最能抑制過氧化氫的分解。而且，由實驗例20的結果得知，含有構造中不具有氮原子的膦酸系螫合劑之蝕刻劑(蝕刻劑22)，在長時間連續使用該蝕刻劑時，過氧化氫會急速分解，而難以長時間持續使用。 From the results of Experimental Examples 17 to 19, it is understood that the chelating agent of the present invention is etched with di-ethyltriamine penta (methylene phosphonic acid) in terms of the decomposition inhibiting effect of hydrogen peroxide. An etchant (etchant 21) and an etchant (etchant 21) containing nitrosole (methylene phosphonic acid) are preferred, and an etchant (etchant 21) containing nitrosole (methylene phosphonic acid) is most preferred. It can inhibit the decomposition of hydrogen peroxide. Further, as a result of Experimental Example 20, it was found that an etchant (etching agent 22) containing a phosphonic acid-based chelating agent having no nitrogen atom in the structure rapidly decomposes hydrogen peroxide when the etchant is continuously used for a long period of time. It is difficult to continue to use for a long time.
由以上的結果，只有組合(B)構造中具有氮原子的膦酸系螫合劑與(D)具有至少1個羥基及至少3個羧基的有機酸之本發明的蝕刻劑，不會降低Ti/Cu的溶解速度比，最能抑制(防止)過氧化氫的分解，得知結果係因為溶液壽命變長，而成為可長時間連續使用的蝕刻劑。而且得知，本發明的蝕刻劑因為具有適度的蝕刻速度，而成為蝕刻速度容易控制之蝕刻劑。 From the above results, only the phosphating agent of the present invention having a nitrogen atom-containing phosphonic acid-based chelating agent and (D) an organic acid having at least one hydroxyl group and at least three carboxyl groups in combination with the structure (B) does not lower Ti/ The dissolution rate ratio of Cu is the most effective to suppress (prevent) the decomposition of hydrogen peroxide, and as a result, the etchant which can be continuously used for a long period of time is obtained because the life of the solution is prolonged. Further, it has been found that the etchant of the present invention has an appropriate etching rate and is an etchant which is easy to control the etching rate.
本發明的蝕刻劑，係Ti系金屬以及具有該Ti系金屬的半導體基板之Ti系金屬加工用蝕刻劑，更詳細而言，係作為於Ti系金屬的上部具有金屬銅或銅合金的半導體基板上之Ti系金屬的蝕刻劑之較理想的蝕刻劑。 The etchant of the present invention is a Ti-based metal and a Ti-based metal working etchant for a semiconductor substrate having the Ti-based metal, and more specifically, a semiconductor substrate having a metal copper or a copper alloy on the upper portion of the Ti-based metal. An ideal etchant for the Ti-based metal etchant.
本發明的蝕刻方法，係適合於具有Ti系金屬的半導體基板之Ti系金屬的加工之蝕刻方法，更詳細而言，係適合於選擇性地蝕刻具有Ti系金屬以及於該Ti系金屬的上部之金屬銅或銅合金的半導體基板上的Ti系金屬的蝕刻方法。 The etching method of the present invention is an etching method suitable for processing a Ti-based metal of a semiconductor substrate having a Ti-based metal, and more specifically, is suitable for selectively etching a Ti-based metal and an upper portion of the Ti-based metal. A method of etching a Ti-based metal on a semiconductor substrate of a metal copper or a copper alloy.
本發明的蝕刻劑調製液，係藉由與包含過氧化氫所成的溶液混合，而可成為本發明的蝕刻劑者，為適合於臨用時調製本發明的蝕刻劑之調製液。 The etchant preparation liquid of the present invention can be used as an etchant of the present invention by mixing with a solution containing hydrogen peroxide, and is a preparation liquid suitable for preparing the etchant of the present invention at the time of use.
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| CN110462799A (en) * | 2017-03-31 | 2019-11-15 | 关东化学株式会社 | The etchant and engraving method of titanium layer or titanium-containing layer |
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